WO2005063887A1

WO2005063887A1 - Resin blend composition, sheet and heat-shrinkable sheet comprising the resin blend composition, and shrink label and package obtained with the heat-shrinkable sheet

Info

Publication number: WO2005063887A1
Application number: PCT/JP2004/019568
Authority: WO
Inventors: Kouichirou Taniguchi; Takeyoshi Yamada; Toshiaki Ebitani
Original assignee: Mitsubishi Plastics, Inc.
Priority date: 2003-12-25
Filing date: 2004-12-27
Publication date: 2005-07-14
Also published as: GB2425127B; GB0614660D0; GB2425127A

Abstract

[PROBLEMS] To obtain a resin blend composition having transparency, impact resistance, flowability, etc. [MEANS FOR SOLVING PROBLEMS] The resin blend composition comprises 1 to 99% by mass polycarbonate resin (b-1) and 1 to 99% by mass polyester resin (b-2), the polyester resin (b-2) being a polyester resin comprising: carboxylic acid monomer units (i) in which 80 to 100 mol% of all the units (i) are accounted for by aromatic dicarboxylic acid units; and glycol monomer units (ii) in which 0.1 to 40 mol% of all the units (ii) are accounted for by 1,4-CHDM units and 0.5 to 15 mol% of all the units (ii) are accounted for by polyalkylene glycol units having a number-average molecular weight of 500 to 3,000.

Description

Mixed resin composition, sheet and heat-shrinkable sheet using the mixed resin composition, and shrinkable label and package using the heat-shrinkable sheet

Technical field

The present invention relates to a mixed resin composition, a sheet using the mixed resin composition, and a heat-shrinkable sheet

And a shrinkable label and a package using the sheet. More specifically, a mixed resin composition having transparency, impact resistance, fluidity, and secondary workability, and the mixed resin composition were used. The present invention relates to a sheet and a heat-shrinkable sheet, and a shrink label and a package using the heat-shrinkable sheet.

Background art

[0002] Conventionally, polychlorinated rubber (hereinafter, also referred to simply as "PVC"), which is a resin having transparency and chemical resistance and having a good balance of various physical properties, has been used in various applications. The glass transition temperature can be controlled in a wide range by appropriately selecting and using plasticizers and various compounding agents in accordance therewith, and thus it has been used for various applications. However, PVC resin has a problem that it emits chlorine-containing gas when incinerated after disposal. For this reason, research on alternative materials for PVC is being actively pursued. One of the promising candidate materials for PVC substitutes is polycarbonate resin with excellent transparency and impact resistance. However, sheets and molded articles using this resin were inferior in moldability due to high melt viscosity and low fluidity. Polycarbonate resin also has good heat resistance because it has a higher glass transition temperature than PVC resin, but in the secondary processing temperature range of PVC resin (usually about 50 ° C or more and 100 ° C or less). It was difficult to perform secondary processing (such as vacuum forming or pressure forming).

[0003] In order to solve such problems of the polycarbonate resin, many resin compositions in which a polyester resin is blended with a polycarbonate resin have been conventionally proposed. For example, a polycarbonate resin composition obtained by mixing a polycarbonate resin and a polyester resin such as polybutylene terephthalate and polyethylene phthalate is disclosed in Japanese Patent Application Laid-Open No. 58-18391 (refer to claims). However, the sheets obtained did not satisfy the required transparency. It is made of polycarbonate resin and polyester. It is considered that the transesterification reaction with the fat progressed sufficiently, and the reason was that.

[0004] On the other hand, by controlling the transesterification reaction between a polycarbonate resin and a polyester resin, a resin composition having improved fluidity and excellent transparency, solvent resistance and impact resistance is provided. However, it is difficult to control the transesterification reaction and it is necessary to use a polycarbonate resin having a functional group at a terminal, which is a problem. Was.

[0005] Also, a polyester resin composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol (hereinafter, also simply referred to as "1,4-CHDM"), comprising 1,4C HDM Polyester resin having a power of 0 mol% or more is compatible with polycarbonate resin by simply melt-mixing, and a resin composition having a transparent, single glass transition temperature and good mechanical properties can be obtained. Disc. (UK), 229, 182 (1983).

[0006] However, polyester resins containing 1,4 CHDM in an amount of 40 mol% or more usually have a glass transition temperature of about 80 ° C or more, and the glass transition temperature of a resin composition mixed with polycarbonate resin is reduced. There was a limitation in controlling the temperature of the PVC resin to the secondary temperature range (usually about 50 ° C or more and 100 ° C or less).

[0007] Furthermore, in order to improve the fluidity without impairing the transparency and impact resistance of the polycarbonate resin, the polycarbonate resin is 5 to 95 parts by mass and the polyester resin 5 parts by mass. A mixed resin comprising at least one part of a polyester resin and at least one part by weight of a polyester resin containing at least one kind of polyester resin, a terephthalic acid-based component, a dicarboxylic acid-based polycondensation component, and 1,4 CHDM at 40 mol% or more. A resin composition wherein the weight ratio of the resin is at least 10% of the total polyester resin component balances the force transparency and impact resistance disclosed in JP-A-2002-127488. It was not as satisfying as it could be if it had enough.

[0008] In addition, shrink wrapping and shrink wrapping packaging, heat shrinkable sheets widely used for shrink labels for plastic containers, packaging for preventing destruction and shattering of glass containers, cap seals, etc., are also used as substitutes for Shiori-Dani-Bulle. Materials are needed. The heat-shrinkable sheet has shrink finish, natural shrinkage (shrinkage at a temperature slightly higher than room temperature, for example, The sheet must shrink slightly before its original use.) It is required to have a low rate, transparency, excellent sheet stiffness (rigidity at room temperature), excellent mechanical strength such as rupture resistance, etc. You.

[0009] There is also a demand for an alternative material to vinyl resin for a resin-coated metal sheet used for enhancing the design of interior and exterior, home appliances, furniture and the like. Such a resin-coated metal sheet has a temperature range similar to that of the polychlorinated vinyl. In order to suppress the thermal decomposition of the Shio-Daniel, considering the heat generated by shearing on the calender rolls, the upper temperature limit of the heating was about 200 ° C! It must be able to process. In addition, the sheet for resin-coated metal sheet is required to satisfy the boiling water immersion test, which is one of the evaluation items for the resin-coated metal sheet for building inner layers.

Disclosure of the invention

Problems to be solved by the invention

[0010] An object of the present invention is to provide a mixed resin composition which is suitably used as a substitute material for PVC and which is excellent in transparency, impact resistance, fluidity, and secondary workability, and a sheet using the mixed resin composition. It is to provide.

Another object of the present invention is to provide a heat-shrinkable sheet having excellent mechanical strength such as shrinkage finish, spontaneous shrinkage, transparency, and sheet stiffness (rigidity at ordinary temperature), which is also a substitute for PVC. An object of the present invention is to provide a shrink label and a package using the heat shrinkable sheet.

[0012] Still another object of the present invention is to provide a resin-coated sheet for a metal sheet which also has an excellent substitute for PVC, has excellent calenderability at low temperatures, and has excellent boiling water resistance. Means for solving the problem

The present inventors have conducted intensive studies and as a result, found that a mixed resin composition comprising a polycarbonate resin and a specific polyester resin can solve the above-mentioned problems, and completed the present invention. It led to.

That is, the mixed resin composition of the present invention comprises 1% by mass or more and 99% by mass or less of the polycarbonate resin (bl) and 1% by mass or more and 99% by mass or less of the polyester resin (b-2). In the mixed resin composition comprising: the polyester resin (b-2) is a carboxylic acid monomer As a unit (a), the sulfonic acid monomer unit (a) contains an aromatic dicarboxylic acid unit in an amount of 80 mol% or more and 100 mol% or less. 1 in monomer units (mouth), 4 and 4 0 mol% Cyclohexanedicarboxylic methanol unit 0.1 mole ^_0/0 or cyclohexane, a number average molecular weight of 500 or more 3,000 or less polyalkylene glycol units 0 It is characterized by being a polyester resin containing not less than 5 mol% and not more than 15 mol%.

Here, the polycarbonate resin (b-1) is preferably an aromatic polycarbonate resin.

[0016] The polyester resin (b-2) has a heating rate of 10 ° C by differential scanning calorimetry.

The glass transition temperature, measured in Z minutes, can be between 0 ° C and 50 ° C.

Further, the mixed resin composition has a single glass transition temperature measured at a heating rate of 10 ° CZ by differential scanning calorimetry, and the glass transition temperature is the same as the polycarbonate resin ( It can be a temperature located between the glass transition temperature of b-1) and the glass transition temperature of the polyester resin (b-2).

Further, the mixed resin composition has a glass transition temperature of 50 ° C. or more and 100 ° C. or less measured by differential scanning calorimetry at a heating rate of 10 ° C.Z, or this glass transition. The temperature can be between 100 ° C and 150 ° C.

[0019] The mixed resin composition may be the polycarbonate resin (b-1) in an amount of 75% by mass or more.

95% by mass or less, and 5% by mass or more and 25% by mass or less of the polyester resin (b-2).

[0020] Alternatively, the mixed resin composition comprises the polycarbonate resin (b-1) in an amount of 60% by mass or more and 95% by mass or less, and the polyester resin (b-2) in an amount of 5% by mass or more and 40% by mass or less. The following can be helpful.

[0021] Alternatively, the mixed resin composition comprises 30% by mass or more and 75% by mass or less of the polycarbonate resin (b-1) and 25% by mass or more and 75% by mass of the polyester resin (b-2). It can consist of:

Alternatively, the mixed resin composition comprises 30% by mass or more and 70% by mass or less of the polycarbonate resin (b-1) and 30% by mass or more and 70% by mass or less of the polyester resin (b-2). Less than And can consist of below.

[0023] The sheet of the present invention is characterized by using any of the above mixed resin compositions.

[0024] The heat-shrinkable sheet of the present invention is characterized in that the polycarbonate resin (b-1) is 30% by mass or more and 70% by mass or less, and the polyester resin (b-2) is 30% by mass or more and 70% by mass or less. A sheet comprising the above mixed resin composition comprising: stretching in at least one direction and immersing in hot water at 80 ° C for 10 seconds for at least 20% or more in at least one direction It is characterized by the following.

Here, in the heat-shrinkable sheet of the present invention, the loss tangent (tan δ) curve obtained by performing dynamic viscoelasticity measurement at a vibration frequency of 10 Hz is within a range of 70 ° C. or more and 130 ° C. or less. And a half width of the loss tangent curve may be 15 ° C. or more.

The heat-shrinkable laminated sheet of the present invention has a layer (A) constituting both outer layers, and a layer (B) located between the outer layers, and is stretched in at least one axial direction. A heat-shrinkable laminated sheet having a heat-shrinkage ratio of 20% or more in the main shrinkage direction when immersed in warm water of 10 ° C for 10 seconds, wherein the layer (A) is a thermoplastic polyester resin (a — The resin (B) is composed of a resin composition containing (1) as a main component, and the layer (B) comprises 30% by mass or more and 70% by mass or less of the polycarbonate resin (b-1) and the polyester resin (b). -2) It is characterized by comprising the above mixed resin composition comprising 30% by mass or more and 70% by mass or less.

Here, the thermoplastic polyester resin (a-1) contains 1,4-cyclohexanedimethanol alone in all the glycol monomer units in the thermoplastic polyester resin (a-1). position may be a a 15 mole ^_0/0 to 50 mole ^_0/0 non-crystalline polyethylene terephthalate resin containing less.

[0028] The resin-coated metal sheet sheet of the present invention comprises a polycarbonate resin (b-1) of 60% by mass to 95% by mass, and a polyester resin (b-2) of 5% by mass to 40% by mass. % Or less, characterized in that it is a resin-coated metal sheet using the above mixed resin composition.

The method for producing a sheet for a resin-coated metal sheet of the present invention is a method for producing the sheet for a resin-coated metal sheet, wherein the mixed resin composition is flow-opened by a calendering method. It is characterized by forming at a temperature 10 ° C higher than the starting temperature (T1) and at a temperature from (T1 + 10 ° C) to 200 ° C.

[0030] The resin-coated metal sheet of the present invention is characterized by being covered with the resin-coated metal sheet.

[0031] The shrinkable label of the present invention is characterized in that the heat-shrinkable sheet or any one of the heat-shrinkable laminated sheets is used.

[0032] The package of the present invention is characterized in that the shrinkable label is attached.

[0033] The molded article of the present invention is characterized by using any of the mixed resin compositions described above.

The invention's effect

[0034] According to the present invention, a mixed resin composition which is suitably used as a substitute material for PVC and is excellent in transparency, impact resistance, fluidity, and secondary workability, and a sheet using the mixed resin composition Can be provided.

[0035] Further, according to the present invention, a heat-shrinkable sheet made of a PVC substitute material, having excellent mechanical strength such as shrink finish, natural shrinkage, transparency, and sheet stiffness (rigidity at room temperature), A shrink label and a package using the heat shrinkable sheet can be provided.

Further, according to the present invention, it is possible to provide a sheet for a resin-coated metal sheet that is excellent in PVC substitute material, excellent in calendering at low temperatures, and excellent in boiling water resistance. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

Note that the upper and lower limits of the numerical range in the present invention may be slightly different from the numerical range specified by the present invention, as long as they have the same operational effects as in the numerical range. It is included in the equivalent range.

[0038] [Mixed resin composition]

The mixed resin composition of the present invention comprises a polycarbonate resin (b-1) and a polyester resin (b-2).

The polycarbonate resin (b-1) used in the present invention is preferably an aromatic polycarbonate resin. The aromatic polycarbonate resin (b-11) may be either a homopolymer or a copolymer. In addition, aromatic polycarbonate resin (b-1 1) may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.

[0040] The aromatic polycarbonate resin (b-11) used in the present invention can be produced by any known method such as a phosgene method, an ester exchange method, and a pyridine method. Hereinafter, as one example, a method for producing an aromatic polycarbonate resin by a transesterification method will be described.

[0041] The transesterification method is a production method in which a divalent phenol and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added to carry out melt transesterification polycondensation.

Representative examples of divalent phenols include bisphenols, and 2,2 bis (4-hydroxyphenyl) propane, that is, bisphenol A is particularly preferably used. Also, part or all of bisphenol A may be replaced with another divalent phenol! / ,. Other divalent phenols include bis (4-hydroxyphenol) such as hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1 bis (4-hydroxyphenyl) ethane. ) Alkanes, bis (4-hydroxyphenyl) cycloalkanes such as 1,1 bis (4-hydroxyphenyl) cyclohexane, bis (4-hydro

Compounds such as xyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, 2,2-bis (3-methyl-4-hydroxy) Alkylated bisphenols such as phenol) propane, 2,2 bis (3,5 dimethyl-4-hydroxyphenol) propane, 2,2 bis (3,5-dibromo-4-hydroxyphenol) Examples thereof include halogenated bisphenols such as propane and 2,2 bis (3,5-dichloro-4-hydroxyphenol) propane.

[0042] Representative examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenol) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, and getyl. Carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is particularly preferably used.

The aromatic polycarbonate resin (b-11) used in the present invention has mechanical properties and Taking into account the balance of plasticity, the weight-average molecular weight is usually 10,000 or more, preferably 20 000 or more, and 100,000 or less, preferably <50,000 or less. ! If the weight average molecular weight is 10,000 or more, the mechanical strength of the obtained aromatic polycarbonate resin will not decrease.If the upper limit is 100,000, an appropriate melt viscosity will be obtained, so molding Since processability can be maintained and polymerization can be performed in a relatively short time, it is preferable from the viewpoint of production cycle and cost. In the present invention, the aromatic polycarbonate resin (b-11) may be used alone or in a combination of two or more.

Next, the polyester resin (b-2) constituting the resin composition of the present invention will be described.

The polyester resin (b-2) contains the aromatic dicarboxylic acid unit in the total amount of carboxylic acid monomer units (i) in the range of 80 mol% to 100 mol% as the carboxylic acid monomer unit (ii). In addition, as a glycol monomer unit (mouth), 1,4-cyclohexanedimethanol unit is 0.1 mol% or more and 40 mol% or less in all glycol monomer units (mouth), and the number average molecular weight is 500 or more 3 , containing a 15 mole ^_0/0 hereinafter 000 following polyalkylene glycol unit 0.5 mole ^_0/0 above. The polyester resin (b-2) may contain other carboxylic acid monomer units and other glycol monomer units as long as the above conditions are satisfied! ,.

[0045] The carboxylic acid monomer unit (ii) in the polyester resin (b-2) is the same as the carboxylic acid monomer unit in the polyester resin (b-2). It is desirable that the content of the compound be at least 80 mol%, preferably at least 85 mol%, more preferably at least 90 mol%. The aromatic dicarboxylic acid imparts heat resistance and mechanical strength to the obtained polyester resin (b-2). When the content of aromatic dicarboxylic acid unit is at least 80 mol% in the rubonic acid monomer unit (ii), the resulting polyester resin (b-2) should have good heat resistance and mechanical strength. Become. On the other hand, the upper limit of the content of the aromatic dicarboxylic acid unit is not particularly limited, and the content of the aromatic dicarboxylic acid unit is preferably 100 mol% or less!

[0046] The aromatic dicarboxylic acid used is not particularly limited, but, for example, terephthalic acid, isophthalic acid, naphthalene 1,4 or 2,6-dicarboxylic acid, anthracene dicarboxylic acid , 4,4, diphenyldicarboxylic acid, 4,4, diphenyletherdicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate and the like. Aromatic dicarboxylic acids may be subjected to polymerization as their esters. The aromatic dicarbonate to be used is not particularly limited. For example, the above-mentioned esters of aromatic dicarboxylic acids are preferred. Specifically, lower alkyl esters, aryl esters, ester carbonates, and acid esters are preferred. And Rogenie-danimono.

Here, the carboxylic acid monomer unit (a) may contain a small amount of the aliphatic dicarboxylic acid unit (generally, less than 20 mol%). The aliphatic dicarboxylic acid is not particularly limited, and may be oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecandionic acid, dimer acid, 1,3 or 1,4-cyclohexane. Xandicarboxylic acid, cyclopentanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid and the like are included.

[0048] As described above, the number of glycol monomer units (ports) used in the polyester-based resin (b-2) is 0.1 mol% or more and 40 mol% or less, as described above. It contains 0.5 to 15 mol% of polyalkylene glycol units having an average molecular weight of 500 to 3,000.

[0049] Other glycol monomer units (ports) that are not particularly limited as long as the above conditions are satisfied include, for example, ethylene glycol, diethylene glycol (including by-product components), 1,2-propylene glycol, 3 propanediol, 2,2 dimethyl-1,3 propanediol, trans- or cis 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1, 4 Butanediol, neopentyl glycol, 1,5 pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenolone A , Tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether It is possible to use the unit, such as.

[0050] These can be used alone or in combination of two or more. Further, color tone, transparency, heat resistance, impact resistance and the like can be appropriately imparted to the polyester resin. Considering that the resulting polyester resin can be imparted with thermal stability at the time of molding and that it is inexpensive and easily available industrially, the glycol monomer is an alcohol monomer. It is preferable to use len glycol.

[0051] The 1,4-CHDM unit used in the glycol monomer unit (mouth) mainly gives impact resistance to the resulting polyester resin. Conventionally, when a mixed resin composition is obtained by mixing a polyester resin composed of a terephthalic acid unit, an ethylene glycol unit and 1,4 CHDM units, and a polycarbonate resin, the polyester resin is used. In order to obtain a transparent resin composition having both a single glass transition temperature (Tg) and good mechanical properties by well compatibilizing the polycarbonate resin with 1,4 CHDM units Was typically at least 40 mol% (eg,

Res. Discl. (UK), 229, 182 (1983)). However, 1, 4 polyester榭脂as contained CHDM unit force 0 mole ^_0/0 or more, usually, since Tg is above about 80 ° C, the mixture榭脂composition of polycarbonate-based榭脂It was difficult to control Tg within the temperature range (usually about 50 ° C or higher and 100 ° C or lower) where the secondary processing of PVC resin was performed. As a result of intensive studies, the present inventors have found that a mixed resin composition of a polycarbonate resin and a specific polyester resin has a content of 1,4 CHDM units in the polyester resin. It has been found that they have compatibility even when S is 40 mol% or less.

When the content of 1,4 CHDM units in the polyester resin (b-2) is 0.1 mol% or more in the glycol monomer unit (mouth), the obtained polyester resin (b-2) ) Can be given impact resistance, and if its upper limit is 0 mol%, the effect of lowering the glass transition temperature of the obtained polyester resin (b-2) can be obtained. In the present invention, the content of 1,4 CHDM units is 1 mol% or more, more preferably 10 mol%, in all the glycol monomer units (mouth) in the polyester resin (b-2). It is more than 38 mol%, more preferably, 35 mol% or less. In addition, 1,4 CHDM may be a force in which two types of isomers, cis-type and trans-type, exist.

[0053] The polyalkylene glycol unit having a number average molecular weight of 500 or more and 3,000 or less contained in the glycol monomer unit (mouth) mainly has flexibility and low glass transition in the obtained polyester resin. The temperature (0 ° C or more and 50 ° C or less) is given. When the content of the polyalkylene glycol in the glycol monomer unit (mouth) is 0.5 mol% or more, the resulting polyester resin can be imparted with flexibility and a low glass transition temperature, and the upper limit can be increased. 15 m %, It is possible to suppress a decrease in thermal stability and mechanical strength of the obtained polyester resin (b-2). In the present invention, the content of the polyalkylene glycol having a number average molecular weight of 500 to 3,000 is 1 mol% or more, more preferably 3 mol% or more, in the glycol monomer unit, and It is desirable that the content be 12 mol% or less, more preferably 10 mol% or less.

[0054] The polyalkylene glycol has a number average molecular weight of 500 or more, preferably 800 or more, more preferably 1,000 or more, and desirably 3,000 or less, preferably 2,000 or less. . If the polyalkylene glycol has a number average molecular weight of 500 or more, the resulting polyester resin (b-2) can have sufficient flexibility, and if the upper limit is 3,000, it can be mixed with other components and polymers. , The polymerization reaction is stagnated, and the mechanical strength of the obtained polyester resin can be suppressed from being reduced.

[0055] Further, as the polyalkylene glycol, plural kinds having different number average molecular weights may be used in combination. When a plurality of types are used in combination, it is preferable that the number average molecular weight in a uniformly mixed state is within the above range. The number average molecular weight of the polyalkylene glycol can be measured by a general method such as gel permeation chromatography.

[0056] Examples of such polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polytetramethylene glycol, polyhexamethylene glycol, and the like. Particularly, polytetramethylene glycol is preferred. preferable. These can be used alone or in combination of two or more.

[0057] As described above, the polyester resin (b-2) used in the present invention comprises a carboxylic acid monomer unit (i) containing an aromatic dicarboxylic acid unit in an amount of from 80 mol% to 100 mol%, A single glycol containing 0.1 to 40 mol% of 1,4 CHDM units and 0.5 to 15 mol% of polyalkylene glycol units having a number average molecular weight of 500 to 3,000. It consists of a body unit (mouth). In order to adjust the flexibility, melt viscosity, transparency, mechanical properties, solvent resistance, etc. of the resulting polyester resin, a trivalent or higher polycarboxylic acid compound and Z or a trivalent or higher polyhydric alcohol are further added. May be copolymerized in a small amount (usually, about 0.05 to 12 mol%). [0058] Here, examples of the trivalent or higher polycarboxylic acid conjugate include trimellitic acid, pyromellitic acid and anhydrides thereof, and trivalent or higher polyhydric alcohols include trimethylol. And propane, pentaerythritol, glycerin and the like. These can be used singly or as a mixture of two or more.When only polycarboxylic acid conjugates are used, the content of polycarboxylic acid compound units is used. Is usually at least 0.05 mol%, preferably at least 0.1 mol%, and at most 2 mol%, preferably at most 1 mol%, in the carboxylic acid monomer unit (a). When only a polyhydric alcohol is used, the content of the polyhydric alcohol unit is usually at least 0.05 mol%, preferably at least 0.1 mol%, in the above-mentioned glycol monomer unit (a). There also 2 mol% or less, preferably 1 mole ^_0/0 or less.

[0059] When the polyvalent carboxylic acid conjugate and the polyhydric alcohol are used in combination, the content of the trivalent or higher polyvalent carboxylic acid compound unit in the carboxylic acid monomer unit and the trivalent or higher polyvalent The total of the alcohol unit and the content in the glycol monomer unit is usually at least 0.05 mol%, preferably at least 0.1 mol%, and at most 2 mol%, preferably at most 1 mol%. It is.

If the content of these polycarboxylic acid compound units and / or polyhydric alcohol units is 0.05 mol% or more in each of the above cases, the flexibility and the flexibility of the resulting polyester resin (b-2) can be improved. If the effect of improving the melt viscosity is sufficiently obtained, and if the content is 2 mol% or less, it is difficult to control the reaction due to gelling, and it is also possible to suppress generation of fish eyes in the obtained heat-shrinkable sheet. it can.

[0060] The mixed resin composition of the present invention has a polycarbonate resin (b-1) of 1% by mass to 99% by mass and a polyester resin (b-2) of 1% by mass to 99% by mass. Consists of

The mixing ratio of the polycarbonate resin (b-1) and the polyester resin (b-2) is preferably adjusted as appropriate according to the intended use.

[0061] For example, in order to improve the fluidity without impairing the inherent properties of the aromatic polycarbonate resin such as heat resistance, transparency, and impact resistance, it is necessary to use 75% by mass of the polycarbonate resin (b-1). A mixed resin composition consisting of at least 95% by mass and at least 5% by mass and at most 25% by mass of the polyester resin (b-2)!ヽ. [0062] The secondary resin composition (heat shrinkage, vacuum / pressure forming, etc.) in the secondary processing temperature range of the PVC resin (usually about 50 ° C or higher and 100 ° C or lower) is mixed. In order to apply the mixture to the product, the mixing ratio of the mixed resin composition is 30% by mass or more and 75% by mass or less of the polycarbonate resin (b-1) and 25% by mass or more of the polyester resin (b-2). It is more preferable to select 70% by mass or less so that the total is 100% by mass. More preferably, the polycarbonate resin (b-1) is 40% by mass or more and 70% by mass or less, and the polyester resin (B-1) is b-2) It is desirable to select from 30% by mass to 60% by mass so that the total is 100% by mass.

When the mixed resin composition of the present invention is used for forming a heat-shrinkable sheet, the polycarbonate resin (b-1) has a content of 30% by mass or more and 70% by mass or less, and a polyester resin. Preferably, the mixed resin composition comprises 30% by mass or more and 70% by mass or less of the fat (b-2).

When the mixed resin composition of the present invention is used for forming a resin-coated metal sheet, the content of the polycarbonate resin (b-1) should be 60% by mass or more and 95% by mass or less. It is preferable that the mixed resin composition comprises 5% by mass or more and 40% by mass or less of the polyester resin (b-2).

The mixed resin composition of the present invention has a single glass transition temperature measured by differential scanning calorimetry at a heating rate of 10 ° C.Z, and has a glass transition temperature of a polycarbonate resin (b- It is desirable to be between the glass transition temperature of 1) and the glass transition temperature of the polyester resin (b-2).

Here, that the mixed resin composition has a single glass transition temperature means that the mixed resin composition is measured by a differential scanning calorimeter at a heating rate of 10 ° CZ according to Japanese Industrial Standard JISK 7121 ( This means that when measuring the glass transition temperature using DSC), only one peak showing the glass transition temperature appears. When the mixed resin composition has a single glass transition temperature, the resulting sheet can achieve good compatibility and excellent transparency. Good compatibility can be confirmed by dynamic viscoelasticity measurement and the like in addition to the above DSC measurement.

[0067] Since the aromatic polycarbonate resin has a glass transition temperature of usually about 150 ° C measured by differential scanning calorimetry, for example, the polycarbonate resin (b-1) has a content of 30% by mass or more and 75% by mass or less. And a polyester resin (b-2) of 25% by mass or more and 70% by mass or less In order to provide the mixed resin composition with the secondary processing property in the secondary processing temperature range of the PVC resin (normally, about 50 ° C or more and 100 ° C or less), the mixed resin composition In order to bring the glass transition temperature of the polyester resin (b-b-) to 50 ° C or more and 100 ° C or less, preferably 55 ° C or more and 95 ° C or less, more preferably 60 ° C or more and 85 ° C or less. The glass transition temperature of 2) is preferably from 0 ° C to 50 ° C, more preferably from 5 ° C to 45 ° C. In this case, if the glass transition temperature of the mixed resin composition is 50 ° C or higher, sufficient heat resistance can be obtained immediately.If the glass transition temperature is 100 ° C or lower, heat resistance is good. Yes, and sufficient secondary workability is easily obtained in the secondary processing temperature range of PVC resin. If the glass transition temperature of the polyester resin (b-2) is 0 ° C or higher, the pelletized resin does not become difficult to handle due to blocking. (4) It can exhibit the effect of lowering the glass transition temperature of the resin composition.

[0068] When the mixed resin composition of the present invention is used for forming a resin-coated metal sheet, the mixed resin composition is measured by differential scanning calorimetry at a heating rate of 10 ° CZ. It is preferable that the glass transition temperature is 100 ° C or higher and 150 ° C or lower. In this case, if the mixed resin composition has a glass transition temperature of 100 ° C or more, the boiling water immersion test! This is practically preferable because satisfactory results can be obtained.

[Heat-shrinkable sheet]

Hereinafter, the heat-shrinkable sheet of the present invention will be described. The heat-shrinkable sheet of the present invention can be formed using a polycarbonate resin and a polyester resin. The polyester resin used here is preferably a resin capable of shifting the glass transition temperature derived from the polycarbonate resin to a lower temperature side. Examples of the polycarbonate resin include the above-mentioned polycarbonate resin (b-1), and examples of the polyester resin include the above-mentioned polyester resin (b-2).

[0070] The heat-shrinkable sheet of the present invention is a sheet obtained by stretching a sheet obtained using such a mixed resin composition in at least one direction, and is immersed in hot water at 80 ° C for 10 seconds. It is preferable that the heat shrinkage ratio of at least one direction is 20% or more. Further, the heat shrinkable sheet of the present invention has a loss tangent (tan δ) curve measured by a dynamic viscoelasticity measurement at a vibration frequency of 10 Hz having a single peak within a temperature range of 70 ° C or more and 130 ° C or less. Has the power More preferably, the half width of the loss tangent (tan δ) curve is 15 ° C or more.

In the present invention, the half value width of the loss tangent (tan δ) curve refers to the value of 1 示す 2 of the loss tangent (tan δ における) at the maximum peak temperature of the loss tangent (tan δ) curve. The peak temperature of the loss tangent (tan δ) curve is the first-order change in the value of tan δ with respect to temperature. The temperature at which the differential value becomes zero.

[0072] The heat-shrinkable sheet of the present invention preferably has a single peak in the range of a loss tangent (tan δ) curve force obtained by dynamic viscoelasticity measurement of 70 ° C or more and 130 ° C or less. . If the peak temperature of the loss tangent (tan δ) curve is 70 ° C or higher, the natural shrinkage can be prevented from becoming excessive, good dimensional stability can be imparted, and the Shrinkage due to temperature rise does not become excessive. On the other hand, when the peak temperature force S130 ° C or less of the loss tangent (tan δ) curve is not more than 130 ° C, favorable heat shrinkability can be imparted without lowering the low-temperature stretchability. In the present invention, the peak temperature of the loss tangent (tan δ) curve of the heat-shrinkable sheet is preferably 75 ° C or higher, more preferably 80 ° C or higher, and preferably 125 ° C or lower, more preferably It is desirable that the temperature be 120 ° C or less.

[0073] In the heat-shrinkable sheet of the present invention, the half width of the loss tangent (tan δ) curve is preferably at least 15 ° C. That is, in the present invention, the half width of the loss tangent (tan δ) curve is preferably 15 ° C. or more, more preferably 17 ° C. or more, and particularly preferably 20 ° C. or more. When the half width of the loss tangent (tan δ) curve is 15 ° C. or more, a heat-shrinkable sheet having appropriate compatibility with little decrease in transparency and maintaining good shrinkage finish can be obtained. On the other hand, the upper limit of the half value width of the loss tangent (tan δ) curve is not particularly limited, but it is possible to prevent a decrease in transparency of the sheet due to a decrease in compatibility between the polycarbonate resin and the polyester resin. In order to reduce the loss tangent (tan δ) curve, the half width of the curve should be 40 ° C or less, preferably 35 ° C or less, more preferably 32 ° C or less, and most preferably 30 ° C or less! /.

[0074] The loss tangent (tan δ) curve of the heat-shrinkable sheet has a single peak in the temperature range of 70 ° C to 130 ° C, and the half-value width of the loss tangent (tan δ) curve is In order for the mixed resin composition used for sheet formation to have a loss tangent (tan δ) curve of 70 ° C or higher, the temperature must be 15 ° C or higher. It is desirable that a single peak exists within a temperature range of 130 ° C or lower and that the half width of the loss tangent (tan δ) curve is 15 ° C or higher. In the present invention, the polycarbonate resin (b-1) and the polyester resin (b-2) are mixed by appropriately adjusting the mixing ratio and the like in consideration of the degree of compatibility and the like. The shape and half width of the loss tangent (tan δ) curve of the entire resin composition can be adapted to the above conditions. For example, when a polycarbonate resin having a relatively high Tg is used, a relatively large amount of a polyester resin capable of shifting the Tg of the polycarbonate resin to a lower temperature side can be used to form a mixed resin. By suppressing the rapid thermal shrinkage by lowering the Tg of the entire composition, the shape and half width of the loss tangent (tan δ) curve of the mixed resin composition are adjusted to the above conditions, that is, the curve is 70 ° C or higher. It has a single peak in the temperature range below ° C and can be adapted to the condition where the half width is 15 ° C or more.

[0075] The peak temperature and the half width of the loss tangent (tan δ) curve obtained by dynamic viscoelasticity measurement can be obtained by the following method. That is, an object to be measured (heat-shrinkable sheet, etc.) Force A sample of 4 mm long and 60 mm wide was cut out, and the vibration frequency was 10 Hz using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.). , Strain 0.1%, temperature rise rate 3 ° CZ, 25mm between chucks, start measurement at 50 ° C in the horizontal direction, and measure (E ') and loss modulus (E ") From the obtained data, a loss tangent (tan δ = Ε "ΖΕ ') curve is obtained, and the peak temperature of the loss tangent curve and its half-value width are obtained.

When the heat-shrinkable sheet of the present invention is formed using, for example, a non-crystalline polyester resin or a relatively low-crystalline polyester resin, a loss tangent (tan δ) curve is obtained. The loss tangent value at the peak temperature is preferably 1.5 or less, more preferably 1.4 or less, and particularly preferably 1.2 or less.

[0077] [Heat-shrinkable laminated sheet]

Hereinafter, the heat-shrinkable laminated sheet of the present invention will be described. The heat-shrinkable laminated sheet of the present invention has a (Α) layer constituting both outer layers, and a (Β) layer located between the outer layers.

[0078] The (は) layer is a resin composition resin mainly composed of a thermoplastic polyester resin (a-1) containing at least one carboxylic acid monomer unit and at least one glycol monomer unit. Planar Examples of the carboxylic acid monomer unit contained in the thermoplastic polyester resin (a-1) include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, and 2-methyl Terephthalic acid, 4,4 stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6 naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane , Anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, aromatic dicarboxylic acid units such as 5-Na sulfoisophthalic acid, ethylene bis p-benzoic acid, adipic acid, sebacine Aliphatic diacids such as acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Examples thereof include a carboxylic acid unit, and among them, a terephthalic acid unit is preferable. These carboxylic acid monomer units may be used alone or in a combination of two or more.

[0080] Examples of the glycol monomer unit contained in the thermoplastic polyester resin (a-1) include diethylene glycol, ethylene glycol, 1,2 propylene glycol, and 1,3 propanediol. , 2,2 dimethyl-1,3 propanediole, trans- or cis-1,2,2,4,4-tetramethyl- 1,3-cyclobutanediol, 2,2,4,4-tetramethyl- 1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5 pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol , Decamethylene glycol, cyclohexanediol, p-xylene diol, bisphenol A, tetrabromobisphenol 8, tetrabromobisphenol A bis (2-hydroxy Chirueteru) include units such as, among others Echire glycol units and 1, the 4-cyclohexylene Cyclohexanedicarboxylic methanol units preferable. These glycol monomer units may be used alone or in combination of two or more.

The thermoplastic polyester resin (a-1) containing a strong carboxylic acid monomer unit and a glycol monomer unit includes polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene Terephthalate resin, polyethylene isophthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polyethylene terephthalate Z-isophthalate copolymer resin, _Χ) 4-cyclohexanedimethanol unit in total glycol unit Amorphous polyethylene terephthalate榭脂like contained in the body unit 15 mole ^_0/0 to 50 mole ^_0/0 or the like. A high melting point and high crystalline aromatic polyester as the hard segment, and a thermoplastic polyester elastomer composed of carbon such as amorphous polyester and amorphous polyether as the soft segment should be appropriately mixed and used. You can also. These may be used alone or in combination of two or more.

[0082] In the present invention, as the thermoplastic polyester resin (a-1), 1,4-cyclohexane dimethanol unit is the total glycol unit of the thermoplastic polyester resin (a-1). amorphous polyethylene terephthalate榭脂containing in mer units 15 mole ^_0/0 to 50 mole ^_0/0 or less is preferably used. The amorphous polyethylene terephthalate resin is obtained by mainly using terephthalic acid as a carboxylic acid monomer and mainly using ethylene glycol and 1,4 CHDM as a glycol monomer.

Here, in the amorphous polyethylene terephthalate resin, the content of 1,4 CHDM units is preferably 15 mol based on all glycol monomer units of the thermoplastic polyester resin (a-1). %, More preferably at least 20 mol%, preferably at most 50 mol%, more preferably at most 40 mol%. When the content of the 1,4-CHDM unit is 15 mol% or more, the printability problem due to crystallization is less likely to occur, and the brittleness over time can be suppressed. On the other hand, if the upper limit is 50 mol%, a good film-forming property without excessively high viscosity during extrusion melting can be obtained. It should be noted that 1,4 CHDM has two types of isomers, cis-type and trans-type.

The heat-shrinkable laminated sheet of the present invention has an intermediate layer (B) between both outer layers (A) constituting the surface layer and the back layer. This (B) layer is a mixed resin composition comprising 30% by mass or more and 70% by mass or less of a polycarbonate resin (b-1) and 30% by mass or less and 70% by mass or less of a polyester resin (b-2). Is used. The polyester resin (b-2) has an aromatic dicarboxylic acid unit of 80 mol% or more and 100 mol% or less as a carboxylic acid monomer unit, and 1,4 CHDM units as a glycol monomer unit. 1 mol% to 40 mol%, and 0.5 mol% to 15 mol% of polyalkylene glycol units having a number average molecular weight of 500 to 3,000.

In addition, the polyester resin (b-2) may be used as long as other carboxylic acid mono- It may contain body units and other glycol monomer units.

[0085] The polycarbonate resin (b-1) forming the layer (B) is an aromatic polycarbonate resin.

(b-11) is preferred. The layer (B) is a polycarbonate resin (b-1) and a polyester resin (b-2), which are preferably formed using the mixed resin composition of the present invention. Is mentioned.

[0086] The thermoplastic polyester resin (a-1) and the polyester resin (b-2) used in the present invention each have moldability and sheetability within a range not to impair the effects of the present invention. For the purpose of improving and adjusting the physical properties, etc. of other resins, other resins such as polyester resin, polyether, polyamide, polyolefin, polymethyl methacrylate, core-shell type, graft type or linear random and block. Rubber-like modifiers such as copolymers, inorganic particles such as silica, talc, olefins, calcium carbonate, pigments such as titanium oxide and carbon black, flame retardants, weather resistance stabilizers, heat resistance stabilizers, Additives such as an anti-decomposition agent (such as a monomer or polymer of a carbodiimide compound), an anti-static agent, a melt viscosity improver, a cross-linking agent, a lubricant, a nucleating agent, a plasticizer, and an anti-aging agent can be appropriately added.

[0087] The thermoplastic polyester resin (a-1) and the polyester resin (b-2) used in the present invention can each be produced by a known direct polymerization method, transesterification method, or the like. If necessary, esterification catalysts such as titanium butoxide, dibutyl tin oxide, magnesium acetate, and manganese acetate, transesterification catalysts, titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, and disulfide Polymerization catalysts such as tin, antimony trioxide, and germanium dioxide can be used.

[0088] The thermoplastic polyester resin (a-1) and the polyester resin (b-2) were each measured at 30 ° C using tetrachloroethane Z phenol (mass ratio 1Z1) as a solvent. It has an intrinsic viscosity of 0.4 dlZg or more, preferably 0.7 dlZg or more, and 1.5 dlZg or less, preferably 1.2 dlZg or less. When the intrinsic viscosity is 0.4 dlZg or more, the resulting polyester resin does not have a reduced moisture resistance and mechanical strength, while when the upper limit is 1.5 dlZg, polymerization can be performed in a relatively short time. It is preferable in terms of production cycle and cost. In the present invention, these resins may be used alone or as a mixture of two or more. [0089] Layer (B) constituting the heat-shrinkable laminated sheet of the present invention comprises 30% by mass or more and 70% by mass or less of polycarbonate resin (b-1) and 30% by mass of polyester resin (b-2). % Or less and preferably 70% by mass or less. The polycarbonate resin (b-1) is preferably an aromatic polycarbonate resin (b-11). When the polycarbonate resin (b-1) is 70% by mass or less and the polyester resin (b-2) is 30% by mass or more, the glass transition temperature of the mixed resin composition is adjusted to a desired range. Since it can be adjusted and good stretchability can be obtained at a low temperature, the heat shrinkability specified in the present invention can be imparted. On the other hand, if the polycarbonate resin (b-1) is at least 30% by mass and the polyester resin (b-2) is at most 70% by mass, the glass transition temperature of the mixed resin composition will be low. Good spontaneous shrinkage can be obtained without becoming too much, and a moderate seat waist can be obtained. From these facts, in the present invention, the aromatic polycarbonate resin (b-1) is from 40% by mass to 65% by mass, and the polyester resin (b-2) is from 35% by mass to 60% by mass. More preferably, a mixed resin composition is used. In this case, the mixed resin composition comprising the polycarbonate resin (b-l) and the polyester resin (b-2) was measured at a heating rate of 10 ° CZ by differential scanning calorimetry. It is preferable that the glass transition temperature used is single and the glass transition temperature is 50 ° C. or more and 100 ° C. or less.

If the glass transition temperature of the mixed resin composition is 50 ° C. or higher, natural shrinkage of the obtained heat-shrinkable laminated sheet is suppressed, and a sheet having good dimensional stability is obtained, which is practically preferable. On the other hand, if the glass transition temperature is 100 ° C or lower, shrinkage in a relatively short time (several seconds to several tens of seconds) and shrinkage such as shrinkage rate, shrinkage starting temperature, shrinkage gradient, etc. that can achieve high shrink finish can be achieved. It is preferable because characteristics can be easily provided. From these facts, in the present invention, the glass transition temperature of the mixed resin composition comprising the polycarbonate resin (bl) and the polyester resin (b-2) is 55 ° C or more. , More preferably 60 ° C or higher, and 95 ° C or lower, more preferably 85 ° C or lower.

[0091] The aromatic polycarbonate resin used in the layer (B) has a glass transition temperature of about 150 ° C, usually measured by differential scanning calorimetry. Therefore, the content of the polycarbonate resin (b-1) is 30% by mass or more and 70% by mass or less, and the content of the polyester resin (b-2) In order to achieve a glass transition temperature of the mixed resin composition of not less than 50% by mass and not more than 70% by mass, the glass transition temperature of the polyester resin (b-2) should be 0 °. C or higher, more preferably 5 ° C or higher, and desirably 50 ° C or lower, more preferably 45 ° C or lower. When the glass transition temperature of the polyester resin (b-2) is 0 ° C or higher, the occurrence of blocking in the raw material pellets can be suppressed. When the upper limit is 50 ° C, the mixed resin composition can be used. Is preferable because the glass transition temperature can easily be lowered to a predetermined range.

[0092] In the present invention, the mixed resin composition, the heat-shrinkable sheet, and the mixed resin composition, the heat-shrinkable sheet, The layer (A) and the layer Z or (B) of the heat-shrinkable laminated sheet are provided with recycled resin (usually (( B) layer), polyester resins (a-1) and polyester resins other than polyester resins (b-2), such as polyesters, polyethers, polyamides, polyolefins, and polymethyl methacrylates. Rubber-like modifying agents such as core, core, graft or linear random and block copolymers, inorganic particles such as silica, talc, kaolin, calcium carbonate, pigments such as titanium oxide and carbon black, and flame retardants , Weather resistant stabilizer, heat resistant Stabilizer, hydrolysis inhibitor (monomer or polymer of carbodiimide conjugate, epoxy conjugate, oxazoline conjugate, etc.), antistatic agent, melt viscosity improver, crosslinking agent, lubricant, nucleating agent, Additives such as a plasticizer and an antioxidant can be appropriately added.

[0093] In the present invention, a reaction (such as a transesterification reaction) that occurs between the polycarbonate resin (bl) and the polyester resin (b-2) during melt kneading is suppressed as much as possible. This is preferred. If the reaction proceeds excessively, not only the thermal properties of the obtained mixed resin composition deteriorates, but also the foaming phenomenon may appear on the sheet due to coloring or gas generation, which is not preferable. Therefore, the type of catalyst used (a Ge catalyst is preferably used) and the amount of catalyst remaining in the raw material, or the temperature and residence time during melt-kneading, and if necessary, phosphorus-based catalyst It is preferable to pay attention to the addition of a transesterification inhibitor such as a compound (phosphoric acid or phosphorous acid compound). The melt-kneading temperature is appropriately adjusted depending on the flow characteristics, film-forming properties, etc. of the mixed resin composition, but is generally 320 ° C. or lower, preferably 240 ° C. A range of o ° c is preferred.

[0094] The resin composition of the present invention can be formed into a sheet, film, plate or the like by a known method, for example, a method such as an extrusion casting method using a T-die, a calendar method, or an inflation method. Can be. In the present invention, a force that comprehensively describes a film, a sheet, or a plate as a sheet refers to a force in which the written “sheet” refers to any of a film, a sheet, and a plate, or a plurality of these. It shall be determined as appropriate.

[0095] The thickness of the sheet to be formed is not particularly limited, but is usually 5 µm or more and 3,000 m or less. For the melt-kneading, a commonly used single-screw extruder, twin-screw extruder, screwer, mixer and the like can be used. It is preferable to use a twin-screw extruder for uniform dispersion of the mixed resin composition and stability of the mechanical strength of the obtained sheet.

[0096] In the present invention, the obtained sheet can be stretched uniaxially or biaxially. Further, if necessary, the sheet may be subjected to surface treatment or surface treatment such as printing, embossing, electron beam processing, coating, and vapor deposition.

[0097] The sheet using the resin composition of the present invention is excellent in mechanical properties such as transparency, impact resistance, and elongation at break, and has a secondary temperature range of PVC resin (usually, Since it has secondary workability at about 50 ° C or more and about 100 ° C or less, it is suitably used for applications where PVC resin has been applied. For example, used for building materials, interior parts, transparent sheets, resin-coated metal sheet sheets, molding (vacuum / pressure molding, hot press molding, etc.) sheets, coloring plates, transparent plates, shrink sheets, shrink labels, shrink tubes, etc. it can.

[0098] In the case where the mixed resin composition of the present invention is sheet-shaped by a calendering method, the roll set temperature in the calendering method depends on the flow characteristics, roll peeling property, film forming speed of the mixed resin composition. It is preferable to appropriately adjust the mixing resin composition, but the flow starting temperature of the mixed resin composition (Tl) + 10 ° C (T1 + 10 ° C) or higher and 250 ° C or lower, preferably the mixed resin composition The temperature is preferably in the range of not less than + 10 ° C (T1 + 10 ° C) and not more than 200 ° C. In particular, if a film can be formed at a roll set temperature of 200 ° C. or less, existing calendering equipment for flexible polyvinyl chloride can be used without much special modification. Further, by processing at a lower temperature, the influence of hydrolysis or the like can be reduced. In the case of aromatic polycarbonate resin alone, grades with a weight-average molecular weight of 20,000 or more that exhibit stable impact resistance and mechanical strength usually have a flow start temperature of 190 ° C or higher (190 ° C or higher and 205 ° C or lower). At a roll set temperature of 200 ° C or less, stable calendering tends to be difficult.

[0099] In the present invention, preliminary kneading can be performed before calendering.

For the pre-kneading, a commonly used single-screw extruder, twin-screw extruder, kneader / mixer or the like can be used, and is not particularly limited. It is preferable to use a twin-screw extruder in consideration of the stability of the mechanical strength and the transparency of the obtained sheet.

[0100] In the case where the mixed resin composition of the present invention is used to carry out sheeting by a calendering method, it is preferable to add a lubricant in order to improve roll releasability.

Examples of the lubricant used include hydrocarbon lubricants such as paraffin and polyethylene wax, higher fatty acid lubricants such as stearic acid, metal stone lubricants such as calcium stearate, ester lubricants such as montanic acid wax, benzoguanamine, and polystyrene. Organic fine particles such as crosslinked acrylic resin containing methyl methacrylate as a main component are exemplified. In particular, as the organic lubricant which has a synergistic effect with the inorganic lubricant, one having improved external lubricity and having good compatibility with the resin is suitably used. In addition, it is necessary to satisfy conditions such as having thermal stability during melt-kneading, and in the present invention, montanic acid wax is suitably used.

[0101] Here, montanic acid wax refers to montan wax of fossil wax mainly containing fatty acids and fatty alcohols having 21 to 34 carbon atoms obtained by solvent extraction of lignite, and esterification or partial oxidation of this montan wax. This is a wax that has been degraded. Specifically, Hoechst WAX S (manufactured by Hoechst) obtained by oxidizing montan wax, Hoechst WAX E (manufactured by Hoechst), which is a montanic acid diester obtained by esterifying montan wax with ethylene glycol, and montan wax is esterified by glycerin The montanic acid diester, Hostalub WE40 (manufactured by Hoechst), montan wax is partially esterified with butylene glycol, and the remainder is quenched with calcium hydroxide. Hoechst WAX OP (manufactured by Hoechst).

[0102] The amount of the lubricant to be added is 0.05 mass parts or more and 3.0 mass parts with respect to 100 mass parts of the mixed resin composition. Or less, preferably 0.1 to 1.5 parts by mass. At less than 0.05 parts by mass, the effect of improving the roll releasability is small, whereas at more than 3.0 parts by mass, the bleeding on the sheet surface and the mechanical properties of the sheet are reduced. The problem is likely to occur, which is not preferable.

[0103] The heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention are stretched in at least one direction, and have a heat shrinkage of 2 in the main shrinkage direction when immersed in hot water of 80 ° C for 10 seconds. It is important that it is at least 0%.

When the heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention are used for shrink label applications such as PET bottles, the shrinking process can be performed in a relatively short time (about several seconds to about ten and several seconds). As an index, it is an index for determining the adaptability to the shrinking process. For example, the shrinkage required for a heat-shrinkable sheet used for shrink labeling of PET bottles varies depending on the shape. Generally, the force is about 20% to 40%. At present, the shrinking machine that is most frequently used industrially for mounting PET bottle labels is generally called a steam shrinker that uses steam as a heating medium for shrinking! / Puru. In addition, the heat-shrinkable sheet and the heat-shrinkable laminated sheet need to be sufficiently heat-shrinked at a temperature as low as possible from the viewpoint of the influence of heat on the object to be coated.

[0105] In consideration of industrial productivity and the like, the sheet having a heat shrinkage of 20% or more tends to be sufficiently adhered to the object to be coated within the shrinkage processing time. In the present invention, the heat shrinkage when immersed in hot water at 80 ° C for 10 seconds is at least one direction, usually in the main shrinkage direction. It is desirable that the shrinkage ratio is at least 30%, preferably at least 40%, and at most 70%, preferably at most 65%, in at least one direction, usually the main shrinkage direction.

[0106] The heat-shrinkable sheet and heat-shrinkable laminated sheet for use in shrinkable labeling of PET bottles have a heat shrinkage rate when immersed in hot water of 80 ° C for 10 seconds in a direction orthogonal to the main shrinkage direction. It is preferably at most 10%, more preferably at most 7%. In the case of a heat-shrinkable sheet, etc., in which the heat shrinkage in the direction perpendicular to the main shrinkage direction is 10% or less, the dimension itself in the direction orthogonal to the main shrinkage direction after shrinkage decreases, or the printed pattern or character after shrinkage When it is used as a shrink label for square bottles, The occurrence of troubles such as vertical sinks can be suppressed.

[0107] The heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention have a tensile elastic modulus of 1,200 MPa or more in the direction orthogonal to the main shrinkage direction of the sheet from the viewpoint of stiffness (rigidity at room temperature). It is important that the pressure be more than 1,800 MPa, more preferably more than 2, OOOMPa. The upper limit of the tensile modulus of the heat-shrinkable sheet and the heat-shrinkable laminated sheet which is usually used is about 4, OOOMPa, preferably about 3, OOOMPa. If the tensile modulus in the direction perpendicular to the main shrinkage direction of the sheet is 1,500 MPa or more, the stiffness (rigidity at room temperature) of the entire sheet can be increased, and especially when the thickness of the sheet is reduced, However, when a sheet made of a bag such as a PET bottle is covered with a labeling machine or the like, it is preferable because problems such as a decrease in yield and a decrease in sieve due to a break in the seat due to breakage of the seat or the like do not easily occur. The tensile modulus can be measured at 23 ° C. according to JIS K7127.

[0108] Further, the tensile elastic modulus in the main shrinkage direction of the sheet is not particularly limited as long as the stiffness of the sheet is obtained. The force is 1,200MPa or more, preferably 1,800MPa or more, and more preferably 2, OOOMPa or more. The upper limit is about 6, OOOMPa, the preferable upper limit is about 4,500MPa, and the more preferable upper limit is about 4, OOOMPa. By setting the tensile elastic modulus in the main shrinkage direction of the sheet to be 1,200 MPa or more and 6,0 MPa or less, the stiffness of the sheet in both directions can be increased!

[0109] The rupture resistance of the heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention is evaluated by tensile elongation at break. The elongation in the direction (MD) is at least 100%, preferably at least 200%, more preferably at least 300%. When the tensile elongation at break in an environment of 0 ° C. is 100% or more, problems such as breakage of the sheet during processes such as printing and bag-making occur, which is preferable. In addition, when the tensile force applied to the sheet increases with the speeding up of processes such as printing and bag-making, it is more preferable that the tensile elongation at break is 200% or more, so that the sheet is difficult to break.

[0110] The seal strength of the heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention is a method of peeling at a test speed of 200 mmZ in the main shrinkage direction by a T-type peeling method in an environment of 23 ° C and 50% RH. When measured by using, the width is 3 NZ15 mm or more, preferably 5 NZ15 mm or more, more preferably 7 NZ15 mm or more. The upper limit of the sealing strength is not particularly limited, but is preferably about 15 NZ 15 mm width from the viewpoint of the solvent resistance of the sheet surface.

[0111] The sheet, the heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention have a transparency, for example, when a sheet having a thickness of 50 µm is measured according to JIS K7105, the total haze is usually 10% or less. Is more preferably 7% or less, particularly preferably 5% or less. If the total haze is 10% or less, a clear display effect can be obtained.

[0112] The natural shrinkage of the heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention is desirably as small as possible. Generally, the natural shrinkage of the heat-shrinkable sheet and the like is, for example, 30 days at 30 ° C. It is desirable that the natural shrinkage after storage is 2.0% or less, preferably 1.5% or less, and more preferably 1.0% or less. If the natural shrinkage ratio under the above conditions is 2.0% or less, even if the produced sheet is stored for a long period of time, it can be stably mounted on a container or the like, so that practical problems hardly occur.

Next, the perforation cutability of the heat-shrinkable laminated sheet of the present invention will be described.

Here, perforations are used to impart easy-opening properties to cap seals and labels attached to plastic bottles, glass bottles, etc. by heat shrinkage, and to make it easy to peel off bottles and bottles during recycling. Perforations are usually provided in advance with one or two or more perforations. Perforation processing is usually performed using a perforation blade at the time of center sealing. The perforation length and the distance between the perforations are generally about lmm or about 0.7 mm, respectively. The force is not limited to this.

[0114] The thickness of the heat-shrinkable laminated sheet of the present invention is not particularly limited, but is usually 5 m or more, preferably 20 µm or more, and 100 µm or less, preferably 80 µm or less. m or less. Here, when the thickness of the heat-shrinkable laminated sheet is 5 μm or more, the handling property of the sheet is good, and when it is 100 m or less, the shrinkage property is good, and It is economically favorable. In addition, the heat-shrinkable laminated sheet of the present invention may be subjected to surface treatment and surface treatment such as corona treatment, printing, coating, and vapor deposition, as well as bag making and perforation using various solvents and heat seals, as necessary. And so on. [0115] The thickness of each layer constituting the heat-shrinkable laminated sheet of the present invention is not particularly limited as long as it is set in consideration of the above-described effects and functions. For example, the (A) layer Z ( B) Layer Z The thickness ratio of the (A) layer is preferably in the range of 1Z2Z1-1Z12Z1, and more preferably in the range of 1/3 / 1-1Z1OZ1. When the thickness ratio of the intermediate layer (B) is less than S1Z2Z1, the effect of improving the shrinkage finish and perforation cutability is not remarkable. Further, the polycarbonate resin (b-l) forming the layer (B) is generally inferior in solvent resistance required at the time of printing. Therefore, it is preferable to mix a polyester resin (b-2). , (A) are preferably laminated as outer layers. In consideration of this, the thickness of the layer (A) is preferably 1 μm or more, more preferably 3 μm or more, and the upper limit is more preferably 20 μm or less. ! / ,.

Next, a method for producing the sheet, the heat-shrinkable sheet, and the heat-shrinkable laminated sheet of the present invention will be described. The sheet, heat-shrinkable sheet and heat-shrinkable laminated sheet of the present invention can be produced by a conventionally known method.

The form of the sheet may be flat or tubular, but it is flat in terms of productivity (a number of products can be cut in the width direction of the raw sheet) and printing on the inner surface. A planar shape is more preferable.

[0117] For example, a method for manufacturing a planar laminated sheet will be described. For example, using a plurality of extruders, each resin as a raw material is melt-kneaded, co-extruded from a T-die, and chilled (cast roll). Cool and solidify to form a laminate, then roll stretch in the machine direction and tenter stretch in the transverse direction, and then uniaxial or biaxial by annealing, cooling, and if necessary, corona discharge treatment. A laminated sheet stretched in the direction can be manufactured. Further, a tubular sheet manufactured by the tubular method may be cut out to be flat. Here, the resin composition or the like as a raw material may be melt-kneaded and cut into pellets, for example, and the pellet-shaped resin composition may be melt-extruded again and heated. A shrinkable laminated sheet can also be manufactured.

[0118] For melt-kneading, generally used single-screw extruders, twin-screw extruders, kneader mixers, and the like can be used, and are not particularly limited. Considering the uniform dispersibility of the mixed resin composition, the stability of the mechanical strength and the transparency of the resulting heat-shrinkable sheet, twin-screw extrusion It is preferable to use a machine.

[0119] In the present invention, it is preferable to suppress as much as possible the reaction (eg, transesterification reaction) that occurs during melt-kneading. That is, the polycarbonate resin (b-1) and the polyester resin (b-2) constituting the layer (B), and the thermoplastic polyester resin (a-) added as Z or recycled resin or the like. It is preferable to minimize the reaction (e.g., transesterification reaction) occurring between 1).

[0120] If the reaction proceeds excessively, thermal properties of the obtained mixed resin composition may deteriorate, or a foaming phenomenon may appear on the melt-extruded sheet due to coloring or gas generation, which is not preferable. Therefore, it is preferable to pay attention to the type of catalyst of the raw material to be used (a Ge-based catalyst is preferably used) and the amount of the catalyst remaining in the raw material, or the temperature and residence time during melt-kneading. It is also preferable to add a transesterification inhibitor such as a phosphorus compound (phosphoric acid or phosphorous acid compound) if necessary.

[0121] For example, when the T-die method is used, the molding temperature is set to a force appropriately adjusted depending on the flow characteristics, film forming properties, and the like of the mixed resin composition. A range is preferred. The melt-extruded resin is cooled by a cooling roll, air, water, etc., and then reheated by an appropriate method such as hot air, hot water, infrared ray, microwave, etc., and roll method, tenter method, tubular method, etc. Thereby, it is stretched in a uniaxial or biaxial direction.

[0122] The stretching temperature is a force that needs to be changed depending on the glass transition temperature of the resin composition to be used and the characteristics required for the heat-shrinkable sheet. Generally, the temperature is from 60 ° C to 130 ° C, preferably from 70 ° C to 120 ° C. It is controlled within the range of ° C or less. The stretching ratio is 1.5 to 10 times, preferably 1.7 times, in the main shrinkage direction, depending on the properties of the resin composition to be used, the stretching method, the stretching temperature, the desired product form, and the like. Within the range of 7 times or less, it is appropriately determined in the uniaxial and Z or biaxial directions. Even in the case of uniaxial stretching in the transverse direction, it is effective to impart a weak stretch of about 1.05 to 1.8 times in the longitudinal direction for the purpose of improving the mechanical properties of the sheet. Next, the stretched sheet is subjected to a heat treatment or a relaxation treatment at a temperature of about 50 ° C or more and 100 ° C or less, as necessary, for the purpose of reducing the natural shrinkage rate and improving the heat shrinkage property, and the like. The sheet is rapidly cooled within a period in which the molecular orientation is not relaxed, and becomes a heat-shrinkable sheet.

[Sheet for resin coated metal sheet] The resin-coated metal sheet of the present invention,

A resin-coated metal sheet can be formed using the mixed resin composition of the present invention. The resin-coated metal sheet sheet of the present invention has a polycarbonate resin (b-1) of 60% by mass or more and 95% by mass or less, and a polyester resin (b-2) of 5% by mass or more and 40% by mass or less. It is necessary to be formed by using a mixed resin composition comprising a polycarbonate resin (b-1) of 65% by mass or more and 90% by mass or less and a polyester resin (b-2). ) Is preferably formed using a mixed resin composition comprising 10% by mass or more and 35% by mass or less. Polycarbonate resin is a mixed resin composition in which the mixing amount of the polycarbonate resin (b-1) is 95% by mass or less and the mixing amount of the polyester resin (b-2) is 5% by mass or more. Since the flow start temperature of the system resin (b-l) can be appropriately reduced, calendering can be performed using a calendering facility for a soft polychlorinated bur. That is, the bank (mixed resin composition) can rotate regularly and stably in the processing equipment.

[0124] When the mixing amount of the polycarbonate resin (b-1) is 60% by mass or more and the mixing amount of the polyester resin (b-2) is 40% by mass or less, the obtained mixed resin composition can be obtained. Since the glass transition temperature of the product does not drop significantly, satisfactory results can be obtained by a boiling water immersion test, and the mechanical strength such as tensile elongation at break does not decrease, so that the secondary workability decreases. Not even. Therefore, secondary processing such as bending can be applied to the obtained resin-coated metal plate.

[0125] In the present invention, a laminate can be formed using the mixed resin composition of the present invention. For example, a layered product can be formed by laminating a layer composed of another material from the layer composed of the mixed resin composition of the present invention, or a heat-shrinkable laminated sheet. The laminated body may have a configuration in which a layer made of the mixed resin composition of the present invention is used as an intermediate layer, and outer layers on both sides of the layer are made of another material.

[0126] The resin-coated metal sheet of the present invention can be manufactured by a known method, for example, an extrusion casting method using a T-die, a calendering method, an inflation method, or the like. The calendar processing method is preferred in view of the response to multi-product small-lot production including color change.

[0127] The thickness of the resin-coated metal sheet of the present invention is not particularly limited, but is usually 50 μm or more and 500 μm or less. When the thickness of the sheet is less than 50 μm, when used for a resin-coated metal plate, the performance as a protective layer for the metal plate and the embossability are poor. It is not preferable because the secondary curability such as punching tends to be inferior. Further, if necessary, the sheet can be subjected to a surface treatment such as printing, embossing, electron beam processing, coating, vapor deposition, or surface treatment.

[0128] The obtained resin-coated metal sheet can be used after being colored with a pigment or the like. A sheet having excellent transparency is suitably used as an oversheet of a printed resin-coated metal sheet. Can be Here, the haze (haze value), which is an index of transparency, is preferably smaller, but when the thickness of the sheet is 150 m, it is usually 5% or less, preferably 4% or less. If present, it can be used as an oversheet of a resin-coated metal plate on which printing has been performed without deteriorating its design, visibility, display effect, and the like.

[0129] Next, as a method for bonding the resin-coated metal sheet of the present invention to a metal plate, a method using an adhesive, a method of heat-sealing without using an adhesive, a method of extrusion coating, and the like. For example, there is a method of applying a polyester-based or epoxy-based adhesive to the surface of the metal plate to be bonded to the resin-coated metal plate sheet to cover the resin sheet.

[0130] In this method, a commonly used coating equipment such as a reverse coater or a kiss coater is used for the metal plate, and the adhesive film after drying is applied to the metal surface on which the resin-coated metal plate sheet is to be bonded. The coating surface is dried and heated by an infrared heater and a hot air heating furnace, and the surface temperature of the metal plate is adjusted to the flow start temperature of the resin-coated metal sheet + 10 The resin-coated metal sheet can be obtained by immediately covering and cooling the sheet with a roll laminator while maintaining the temperature at about ° C or higher.

[0131] Examples of the metal sheet used for the resin-coated metal sheet of the present invention include various steel sheets such as a hot-rolled steel sheet, a cold-rolled steel sheet, a molten zinc plated steel sheet, an electric zinc plated steel sheet, a tin plated steel sheet, a stainless steel sheet, and the like. A plate can be used, and may be used after performing a normal chemical conversion treatment.

[0132] [Shrink label and package]

The heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention each have an excellent shrink finish. It has mechanical strength such as resilience, natural shrinkage, transparency, sheet stiffness (rigidity at room temperature), perforation cutability, etc., and its use is not particularly limited. (Round and square bottles of about 300 ml to 12 liters) for shrink label applications, shrink packaging for various foods and goods, shrink bundling packaging, cap sealing for various containers, shrink tubing for various foods and goods, etc. It can be suitably used as a shrink label, and a package with the shrink label attached can be obtained. Then, the shrink label and the package of the present invention can be manufactured by using a usual method.

[0133] The heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention each have excellent shrinkage finish and shrinkage properties, so that the heat-shrinkable label material of a plastic molded article that is deformed when heated to a high temperature. In addition, a material whose thermal expansion coefficient, water absorption and the like are very different from those of the heat-shrinkable laminated sheet of the present invention, for example, metal, porcelain, glass, paper, polyethylene, polypropylene, polyolefin resin such as polybutene, polymethacrylic resin Heat of a package (container) using at least one selected from acid ester resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and polyamide resin as a constituent material It can be suitably used as a shrinkable label material.

[0134] In addition to the above resins, polystyrene, rubber-modified impact-resistant polystyrene (HIPS), styrene, and the like may be used as the material constituting the plastic package in which the heat-shrinkable sheet or the heat-shrinkable laminated sheet of the present invention can be used. Butyl acrylate copolymer, styrene acrylonitrile copolymer, styrene maleic anhydride copolymer, acrylonitrile butadiene styrene copolymer (ABS), methacrylate butadiene styrene copolymer (MBS), polychloride copolymer Cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like can be mentioned. These plastic packages may be a mixture of two or more resins or a laminate.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these. Various measurements and evaluations of the resin, sheet, film, and the like displayed in the present specification were performed as follows. Here, the direction of flow of the sheet (film) from the extruder or calendering machine is defined as the longitudinal direction (MD), and TD).

[0136] (1) Glass transition temperature (Tg)

Using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer Co., Ltd., according to JIS K7121, a 10 mg sample was heated from -40 ° C to 250 ° C at a heating rate of 10 ° CZ, and then heated to 250 ° C. After cooling for 1 minute, the cooling rate is lowered to 40 ° C in 10 ° CZ minutes, and after holding for 1 minute at 40 ° C, the thermogram force when the heating rate is raised again in 10 ° CZ minutes is also The glass transition temperature (Tg) was determined.

[0137] (2) Composition analysis of polyester resin

A solution prepared by dissolving a polyester resin in form (solvent) of heavy-duty mouth (sample concentration: 100 mg, 1 ml solvent) shall be used as a sample, and this sample solution shall be monitored for ¹ H by a nuclear magnetic resonance apparatus (NMR). Was analyzed. For the carboxylic acid monomer unit, the mole% was calculated based on the total rubonic acid monomer unit, and for the glycol monomer unit, the mole% was calculated based on the total glycol monomer unit.

[0138] (3) Average refractive index

In accordance with Japanese Industrial Standards JIS K7142, the measurement was performed using sodium D line (589 nm) as a light source and Abago refractometer manufactured by Atago Co., Ltd.

[4] Haze (cloudiness value)

The haze of the obtained sheet was measured according to Japanese Industrial Standard JIS K7105.

[0140] (5) Tensile modulus

According to the Japanese Industrial Standards JIS K7127, the tensile modulus in the lateral direction of the sample was determined under the conditions of a temperature of 23 ° C and a test speed of 5 mmZ.

[0141] (6) Tensile breaking strength, tensile breaking elongation

In accordance with Japanese Industrial Standard JIS K7127, the sample was pulled under the conditions of a temperature of 23 ° C and a test speed of 200 mmZ, and the tensile strength and elongation at break in the lateral direction of the sample were measured.

[0142] (7) Impact resistance

Using a high-speed impact tester (“HTM-1” manufactured by Shimadzu Corporation), a sample piece of 100 mm in the vertical direction and 100 mm in the horizontal direction is fixed with a clamp, and the sample piece is heated at 0 ° C. Center An impact tip with a diameter of 1Z2 inches was dropped at a falling speed of 3 mZ seconds on the sample, and an impact (kgf'mm) was measured when the sample piece was broken.

(8) Flow start temperature

The obtained sheet is cut into small pieces with scissors, dried, and then heated at a heating rate using “Koka Type Flow Tester CFT-500C” manufactured by Shimadzu Corporation (lmm inner diameter, 2 mm long nozzle). The flow start temperature was measured under the conditions of 3 ° CZ and a load of 3.92 MPa (40 kgfZcm ² ).

[0144] (9) Dynamic viscoelasticity measurement

A sample having a size of 4 mm in the vertical direction and 60 mm in the horizontal direction was cut out from the obtained sheet. Using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.), the sample was subjected to a vibration frequency of 10 Hz, a strain of 0.1%, a heating rate of 3 ° CZ, and a chuck distance of 25 mm. In the horizontal direction, the temperature was raised at 50 ° C, and the storage modulus (E ') and the loss modulus (E ") were measured. The obtained data force was also measured by the loss tangent (tan δ). = Ε "ΖΕ ') The number of peaks, the peak temperature, the half width and the peak value of the curve were determined.

(10) Storage modulus (Ε ')

A sample having a size of 60 mm in the vertical direction and 4 mm in the horizontal direction was cut out from the obtained sheet. Using a viscoelasticity measuring device DVA-200 (manufactured by IT Measurement Control Co., Ltd.), this sample was used under the conditions of a vibration frequency of 10 Hz, a strain of 0.1%, a heating rate of 3 ° CZ, and a gap of 25 mm between the chucks. In the vertical direction, the temperature was increased by 50 ° C, and the storage elastic modulus (Ε ') was measured. The obtained data was also determined as the value of storage modulus (Ε ') at 25 ° C.

(11) Heat shrinkage

A sample having a size of 100 mm in the vertical direction and 100 mm in the horizontal direction was cut out from the obtained sheet. After immersing this sample in a hot water bath at 80 ° C for 10 seconds, the amount of shrinkage in the main shrinkage direction (horizontal direction) of the sheet was measured, and the ratio of the amount of shrinkage to the original size before shrinkage was calculated as a percentage. , A minus (1) in the ratio means that it is expanded from its original size.

(12) Natural contraction rate

From the obtained sheet, a sample having a size of 1, OOO mm in the vertical direction and 1,000 mm in the horizontal direction was cut out. After leaving this sample in a thermostat at 30 ° C for 30 days, the main The amount of shrinkage in the shrinking direction (lateral direction) was measured, and the ratio of the amount of shrinkage to the original size before shrinking was determined as a% value.

(13) Shrink finish

The sheet on which grids were printed at intervals of 10 mm in length and width was cut into a size of 100 mm in the vertical direction and 298 mm in the horizontal direction. This cylindrical sheet is attached to a 1.5-liter round plastic bottle and passed through a steam-heated 3m long shrink tunnel for 10 seconds without rotating to cover the sheet. did. However, the temperature of the discharged steam was 99 ° C and the ambient temperature in the tunnel was 90-94 ° C. The sheet covered with the PET bottle was evaluated for shrink finish based on the following evaluation criteria.

Evaluation criteria:

〇Sufficient shrinkage, no cracks, no avatars, no practical grid problem, and good sheet adhesion

X There is clearly a part with insufficient shrinkage, or it has cracks, abata, and noticeable distortion of the lattice.

(14) Calendar workability

Using a φ40πιπι twin screw extruder (LZD = 32), melt and knead at a cylinder setting temperature of 270 ° C, and then transfer it to an L-shaped calendering facility with four rolls of metal rolls with a roll diameter of 250mm. 10 ° C higher than the flow start temperature of the resin composition! ヽ Adjust the temperature within the temperature range (flow start temperature + 10 ° C) to 200 ° C, and visually, based on the following evaluation criteria. The calender film-forming properties were evaluated.

Evaluation criteria:

もの The bank (resin composition) turns regularly and stably, and the resulting sheet has good surface appearance and uniform thickness

X The bank turns irregularly, or the amount of heat is clearly insufficient, and the wound state around the roll is poor.The surface appearance of the sheet may be defective, such as unevenness, or the thickness may be uneven.

(15) Boiling water immersion test A sample cut into a size of 60 mm X 60 mm from a resin-coated metal plate was used. The sample was provided with a 6 mm overhang so that the resin-coated side became convex using an Erichsen test apparatus specified in Japanese Industrial Standard JIS K7121. Thereafter, this sample was immersed in boiling water for 3 hours, and the surface state of the resin sheet of the immersed sample was visually evaluated based on the following criteria.

Evaluation criteria:

全く Power that is completely changeable

X Rough surface, swelling of resin layer, peeling, etc.

[0151] (16) Pencil hardness

Pencil hardness was measured in accordance with the “Pencil pull value” of Japanese Industrial Standard JIS K54008.4 (Testing Machine Method).

[0152] (17) Secondary workability

An impact adhesion bending test was performed on the obtained resin-coated metal plate. Looking at the surface condition of the resin sheet after bending? It was observed and observed, and the secondary workability was evaluated based on the evaluation criteria shown below.

Evaluation criteria:

もの Good with little change

X cracks or cracks

The impact adhesion bending test was performed as follows.力 Cut the sample of 50mm x 150mm each in the length and width direction of the resin coated metal plate, keep it at 23 ° C for 1 hour or more, then bend it to 180 ° (inner bending radius 2mm) using a bending tester Then, a cylindrical weight with a diameter of 75 mm and a mass of 5 kg was dropped on the sample with a height of 50 cm.

(18) Perforation cutability

The heat-shrinkable laminated sheet is perforated (perforation length: 0.7 mm, interval between perforations: 0.7 mm, single line), and the above evaluation of “(13) Shrink finish” is performed. In the same manner as above, attach to a 1.5-liter round PET bottle by heat shrinkage. After cooling to room temperature, the perforated portion was torn by hand, and the perforated cutability was evaluated. However, a cutting test was performed on 10 samples, and the evaluation was performed based on the following evaluation criteria in a sensory test. And evaluated.

Evaluation criteria:

〇 8 or more pieces cut cleanly along perforations

X 3 or more do not cut along the perforation, or 3 or more cut along the perforation, but cut off due to perforation

[Example I]

(Example 1-1)

As shown in Table 1, as a polycarbonate resin (b-l), a dried aromatic polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation, "NOVAREX 7025A", Tg: 149.5 ° C , Average refractive index: 1.5858) (hereinafter may be simply abbreviated as PC) 75% by mass, and as polyester-based resin (b-2), dried transparent soft polyester resin (Mitsubishi Rayon Co., Ltd.) ) Ltd., "DIANITE DN-124", Tg: 19. 1 ° C, carboxylic acid monomers (I) unit: terephthalic acid 100 mol ^_0/0, glycol monomer (mouth) unit: ethylene glycol 66 mol ^_0/0, diethylene glycol 2 mol ^_0/0, 1, 4 Cyclohexanedicarboxylic to Shikuro methanol 26 mole ^_0/0, Sutaira average molecular weight of 1, 000 polytetramethylene glycol 6 mole ^_0/0, the average refractive index: 1. 5461) (hereinafter sometimes abbreviated simply as PET-1) Using a φ40mm co-rotating twin screw extruder (LZD = 36) equipped with a T-die, melt-kneaded at a set temperature of 270 ° C, and mixed at 80 ° C (Examples other than Example I1). In such cases, the temperature of the cast roll was adjusted appropriately at a temperature around the Tg of the mixed resin composition-20 ° C while confirming the state of adhesion of the sheet to the cast roll.) By forming the film, a sheet having a thickness of 150 m was obtained. The obtained sheets were used to evaluate glass transition temperature (Tg), mechanical properties, and the like. The results are shown in Table 1.

(Example I 2)

As shown in Table 1, in Example 1-1, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) was changed. Sheets were obtained in the same manner as in Example 1 except that the amounts were changed to 90% by mass and 10% by mass, respectively. The glass transition temperature (Tg) and mechanical properties were evaluated using the obtained sheet. The results are shown in Table 1. (Example I 3)

As shown in Table 1, in Example 1-1, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) was changed. Sheets were obtained in the same manner as in Example 1 except that the amounts were changed to 95% by mass and 5% by mass, respectively. The obtained sheets were used to evaluate glass transition temperature (Tg) and mechanical properties. The results are shown in Table 1.

(Comparative Example I 1)

As shown in Table 1, in Example 1-1, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) was changed. Sheets were obtained in the same manner as in Example 1 except that the amounts were changed to 100% by mass and 0% by mass, respectively. The glass transition temperature (Tg) and mechanical properties were evaluated using the obtained sheet. The results are shown in Table 1.

(Example I 4)

As shown in Table 2, in Example 1-1, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) was changed. A sheet was obtained in the same manner as in Example 1 except that the mass was changed to 50% by mass and 50% by mass, respectively. Subsequently, the obtained sheet was stretched 3.0 times in the transverse direction at a stretching temperature of 95 ° C using a tenter stretching apparatus, and then rapidly cooled with cold air to obtain a heat-shrinkable sheet having a thickness of 50 m. . Using the obtained sheet and the obtained heat-shrinkable sheet as appropriate, measurement of glass transition temperature (Tg) and evaluation of mechanical properties were performed. The results are shown in Table 2. The heat shrinkage rate was determined by cutting the obtained heat shrinkable sheet to a size of 100 mm in the vertical direction and 100 mm in the horizontal direction, immersing it in a hot water bath at 80 ° C for 10 seconds, measuring the amount of shrinkage in the horizontal direction, The ratio of the amount of shrinkage to the previous original size was calculated as a percentage value. FIG. 1 shows a DSC thermogram of the obtained sheet. Fig. 1 Force As can be seen, the glass transition temperature of this sheet has one peak.

(Comparative Example I2)

As shown in Table 2, in place of PET-1 used as the polyester resin (b-l) in Example I4, an amorphous polyester resin (Eastman Chemical Co., Ltd., “EASTAR PETG Copolyester6763 ", Tg: 79. 0 ° C, carboxylic acid monomers (I) Unit: terephthalic Le acid 100 mole ^_0/0, glycol monomer (mouth) Unit: Ethylene glycol 68 mol ^_0/0, 1, 4- Cyclohexanedicarboxylic methanol 32 mole ^_0/0 cyclohexane, average refractive index: 1.5667) (hereinafter, simply except for using that there is a) abbreviated as PET-2, in the same manner as in example I 4 sheets Got. Subsequently, an attempt was made to stretch the obtained sheet 3.0 times in the transverse direction at a stretching temperature of 95 ° C using a tenter stretching apparatus, but the sheet was broken and could not be stretched. Figure 2 shows the DSC thermogram of the obtained sheet. As is clear from FIG. 2, this sheet has two glass transition temperatures (Tg) at 79.4 ° C. and 134.8 ° C.

[0160] [Table 1]

[0161] [Table 2]

According to Tables 1 and 2, the mixed resin composition consisting of the polycarbonate resin (b-1) and the polyester resin (b-2) and having a single glass transition temperature is the same as the polycarbonate resin. Transparent It can be seen that it has excellent fluidity (Example I13) and secondary workability (Example I4) without significantly impairing features such as lightness and impact resistance.

On the other hand, in Comparative Example I1, which is a polycarbonate resin (b-1) alone, the impact resistance and the transparency were good, but the flowability was poor, and the resin was out of the range specified in the present invention. In Comparative Example 2 which is a resin using a polyester resin, the compatibility with the polycarbonate resin (b-1) is inferior. It can be seen that it is difficult to impart secondary workability (such as heat shrinkability) at a temperature of about 100 ° C or more and 100 ° C or less.

[0163] [Example II]

(Example II-1)

As shown in Table 3, as polycarbonate resin (b-l), a dried aromatic polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation, Novalex 7025A, Tg: 149.5 ° C, average refraction) Rate: 1.5858) (hereinafter may be simply abbreviated as PC) 50% by mass, and as a polyester resin, dried transparent soft polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianite DN-124, tg: 19. 1 ° C, carboxylic acid monomers (I) unit: terephthalic acid 100 mol ^_0/0, glycol monomer (mouth) unit: ethylene glycol 66 mol ^_0/0, Jechire glycol 2 mol ⁰ / _0, 1, 4 Cyclohexanedicarboxylic to Shikuro methanol 26 mole ^_0/0, the number average molecular weight 1, Porite Bok La glycol 6 mole ^_0/0 000, average refractive index: 1.5461, intrinsic viscosity: 0. 94dl / g ) (Hereinafter sometimes abbreviated simply as PET-1) 50% by mass Using a φ40mm co-rotating twin screw extruder (LZD = 36) equipped with a T die, melt-kneading the mixture at a set temperature of 2 70 ° C, and mixing at 50 ° C (except for Example II 1). In Examples, the temperature of the cast roll was adjusted to a temperature of about 20 ° C. (Tg of the resin composition) while confirming the state of adhesion of the sheet to the cast roll. As a result, a cast sheet having a thickness of 150 m was obtained. Subsequently, the obtained sheet was stretched 3.0 times in the transverse direction at a stretching temperature of 95 ° C using a tenter stretching apparatus, and then rapidly cooled with cold air to obtain a heat-shrinkable sheet having a thickness of 50 m. Glass transition temperature (Tg) was evaluated using the obtained cast sheet, and mechanical properties and the like were evaluated using the obtained heat-shrinkable sheet. The results are shown in Table 4. FIG. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

(Example II 2) As shown in Table 3, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) in Example II 1 was 60 mass, respectively. % And 40% by mass, and the stretching temperature was changed to 105 ° C., to obtain a cast sheet and a heat-shrinkable sheet in the same manner as in Example III-1. The Tg was evaluated using the obtained cast sheet, and the mechanical properties and the like were evaluated using the obtained heat-shrinkable sheet. The results are shown in Table 4. FIG. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

(Comparative Example II 1)

As shown in Table 3, the mixing ratio of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) in Example II 1 was 80 mass, respectively. % And 20% by mass, and the stretching temperature was changed to 135 ° C., to obtain a cast sheet and a heat-shrinkable sheet in the same manner as in Example I-1. The Tg was evaluated using the obtained cast sheet, and the mechanical properties and the like were evaluated using the obtained heat-shrinkable sheet. The results are shown in Table 4. FIG. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

(Comparative Example II 2)

As shown in Table 3, an amorphous polyester resin (EASTAR PETG Copolyester6763 manufactured by Eastman Chemical Co., Ltd.) was used in place of PET-1 used as the polyester resin (b-l) in Example II 1. , Tg: 79. 0 ° C, carboxylic acid monomers (I) unit: terephthalic acid 100 mol ^_0/0, glycol monomer (mouth) unit: ethylene glycol 68 mol ^_0/0, 1, to 4 Shiku port Cyclohexanedicarboxylic methanol 32 mole ^_0/0, the average refractive index: 1.5667) (hereinafter, simply PET-2 and were used in place of the substantially serial there be), to obtain a sheet in the same manner as in example II 1 . Subsequently, the obtained sheet was stretched 3.0 times in the transverse direction at a stretching temperature of 95 ° C. using a tenter stretching apparatus, but the sheet could not be stretched because the sheet was broken. The obtained sheet showed Tg at two places, 79.4 ° C and 134.8 ° C.

(Comparative Example II 3)

As shown in Table 3, the cast sheet and the heat-shrinkable sheet were manufactured in the same manner as in Example II 1 except that the PET-2 used in Comparative Example II 2 was changed to the simple substance and the stretching temperature was changed to 90 ° C. To Obtained. Tg was evaluated using the obtained cast sheet, and mechanical properties and the like were evaluated using the obtained heat-shrinkable sheet. The results are shown in Table 4. FIG. 3 shows a loss tangent curve of the obtained heat-shrinkable sheet.

[Table 3]

[0169] [Table 4]

[0170] From Tables 3 and 4, the heat shrinkability obtained by stretching the mixed resin composition of the polycarbonate resin (b-1) and the polyester resin (b-2) specified in the present invention was obtained. The sheet has a peak temperature of tan δ and a half-value width within a predetermined range, and has a mechanical strength such as shrinkage finish, spontaneous shrinkage, transparency, sheet stiffness (rigidity at room temperature), and rupture resistance. (Example II 1 and Example II 2).

On the other hand, in Comparative Example III-l, in which the peak temperature of tan δ where the Tg is high and the tan δ exceeds 130 ° C, it is difficult to impart heat shrinkage, and it is practical to use as a heat shrinkable sheet. I helped to make things impossible. Further, in the case of Comparative Example II-1 using a polyester resin outside the range specified in the present invention, the compatibility with the polycarbonate resin (b-1) was deteriorated. In addition, it was difficult to obtain a heat-shrinkable sheet. Furthermore, in Comparative Example III-3, which is a polyester resin alone, the heat shrinkable sheet obtained by stretching the resin has a narrow half width of tan δ and has a shrink finish. Inferiority helps.

[Example III]

(Example II-1)

As shown in Table 5, as a polycarbonate resin (b-l), a dried aromatic polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation, Novalex 7025A, Tg: 149.5 ° C, average refraction) Rate: 1.5858, flow start temperature: 194.9 ° C) (hereinafter simply abbreviated as PC) 85% by mass, and as a polyester resin (b-2), dried transparent soft polyester resin (Mitsubishi Rayon Co., DIANITE DN- 124, Tg: 19. 1 ° C, carboxylic acid monomers (I) unit: terephthalic acid 100 mol ^_0/0, glycol monomer (mouth) unit: ethylene glycol 66 mole ^_0/0, diethylene glycol 2 mol ^_0/0, 1, 4 Shikuro to Cyclohexanedicarboxylic methanol 26 mol%, a number average molecular weight 1000 polytetramethylene glycol 6 mole ^_0/0, the average refractive index: 1.54 61, intrinsic viscosity : 0.94dl / g) (hereinafter simply abbreviated as PET-1) 15 mass To 100 parts by mass of a mixed composition consisting of the following, 1.0 part by mass of montanic acid wax (Hoechst Co., Ltd., Hoechst WAX OP) was added as a lubricant, and a φ40 mm co-rotating twin screw extruder (LZD = 32) Melt and knead at a cylinder set temperature of 270 ° C using a roll.Then, transfer to an L-shaped calendering facility that has four rolls of metal rolls with a roll diameter of 250mm and roll at a roll set temperature of 200 ° C to obtain a thickness. A 150 m sheet was obtained. Further, a polyester adhesive for a commercially available poly-Shidani-Bull coated metal plate is applied to the metal surface to which the sheet is to be bonded so that the thickness of the dried adhesive film is about 4 m. Then, the coated surface is dried and heated by an infrared heater and a hot-air heating furnace, while maintaining the surface temperature of the zinc-plated steel sheet (0.5 mm thick) at the flow start temperature of the sheet + 10 ° C or more. Immediately, coating and cooling were performed using a roll laminator to obtain a resin-coated metal plate. Glass transition temperature (Tg), mechanical properties, etc. were evaluated using the obtained sheet, and practical tests were evaluated using the obtained resin-coated metal plate. Table 5 summarizes the results. In addition, comprehensive evaluation was performed on the obtained results, and good results were obtained in all of the above evaluations. Show something with symbol "X" did.

(Example m—2)

As shown in Table 5, in Example III, the mixing amount of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) was determined. A sheet having a thickness of 150 / zm was obtained in the same manner as in Example II-1, except that the mass was changed to 70% by mass and 30% by mass, respectively, and the set temperature of the roll was changed to 185 ° C. Using the obtained sheet, a resin-coated metal plate was obtained in the same manner as in Example II. Using the obtained sheet and the obtained resin metal plate as appropriate, evaluation of glass transition temperature (Tg), mechanical properties, and the like, and evaluation of a practical test were performed. Table 5 summarizes the results.

[0173] (Comparative Example II-1)

As shown in Table 5, in Example II-1, the mixing amounts of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) were respectively determined. A sheet having a thickness of 150 / zm was obtained in the same manner as in Example 1 except that the temperature was changed to 50% by mass and 50% by mass, and the set temperature of the roll was changed to 175 ° C. Using the obtained sheet, a resin-coated metal plate was obtained in the same manner as in Example III-1. Using the obtained sheet and resin-coated metal plate as appropriate, evaluation of glass transition temperature (Tg), mechanical properties, and the like, and evaluation of a practical test were performed. Table 5 summarizes the results.

(Comparative Example II—2)

As shown in Table 5, in Example II-1, the mixing amounts of PC used as the polycarbonate resin (b-1) and PET-1 used as the polyester resin (b-2) were respectively determined. It was subjected to calendering in the same manner as in Example III1 except that it was changed to 100% by mass and 0% by mass. However, the winding state around the roll was poor due to the insufficient amount of heat, and the bank was turned irregularly, and it was impossible to obtain a sheet with a good surface appearance.

(Comparative Example III—3)

As shown in Table 5, in Example II-1, 50% by mass of PC used as the polycarbonate resin (b-1) was used as the polyester resin (b-1). Amorphous polyester resin (manufactured by Eastman Chemical Co., Ltd., EASTARPE TG Copolyester6763, Tg: 79.0 ° C, carboxylic acid monomer (a) unit: terephthalic acid 1) 00 mole ^_0/0, glycol monomer (mouth) Unit: Ethylene glycol 68 mol ^_0/0, 1, 4-Cyclohexanedicarboxylic cyclohexane methanol 32 mole ^_0/0, the average refractive index: 1.5667) (hereinafter, simply A sheet having a thickness of 150 / zm was obtained in the same manner as in Example I-1, except that PET-2 (abbreviated as PET-2) was 50% by mass and the roll set temperature was 195 ° C. Using the obtained sheet, a resin-coated metal plate was obtained in the same manner as in Example III-1.

Using the obtained sheet and the obtained resin-coated metal plate as appropriate, evaluation of glass transition temperature (Tg), mechanical properties, and the like, and evaluation of a practical test were performed. Table 5 summarizes the results. The obtained sheet showed two glass transition temperatures (Tg) at 79.4 ° C and 134.8 ° C. Further, the haze of the sheet was 6.5%, which was inferior in transparency.

[0176] (Comparative Example II—4)

As shown in Table 5, in Example II-1, 70% by mass of PC used as the polycarbonate resin (b-1) was used as the polyester resin (b-2). Polyester resin (manufactured by Eastman Chemical Co., Ltd., EASTAR PCTG Copolyester 5445, Tg: 87.3 ° C, carboxylic acid monomer (a)): 100 mol of terephthalic acid ^_0/0, glycol monomer (mouth) unit: ethylene glycol 35 mol ^_0/0, 1, 4-65 mol% hexa Nji methanol cyclohexane) (hereinafter, simply PET-3 and abbreviated) to 30 mass% Except for that, it was subjected to calendering in the same manner as in Example II-1. However, the sheet crystallized during calendering, and it was impossible to obtain a sheet having a good surface appearance. In addition, DSC measurement using the sheet showed a crystal melting peak of 243 ° C.

[0177] [Table 5]

[0178] From Table 5, it can be seen that the resin-coated metal sheet made of the mixed resin composition of the polycarbonate resin and the polyester resin specified in the present invention has high transparency, low-temperature calenderability, and low heat resistance. It can be seen that they are excellent in boiling water, scratch resistance and secondary workability (Example mi, Example III 2).

On the other hand, Comparative Example III 1 having a low glass transition temperature was inferior to the evaluation by the boiling water immersion test, and Comparative Example II-2 of polycarbonate resin alone was inferior in low temperature power renderability.ゝWhen a polyester resin out of the range specified in the present invention is used, the compatibility with the polycarbonate resin is inferior, and the transparency of the obtained sheet is reduced (Comparative Example III-3). However, it can be seen that during calendering at a low temperature, there is a problem such as crystallization of the sheet due to insufficient heat (Comparative Example III4).

[Example IV]

(Example IV-1)

As shown in Table 6, dried amorphous polyester resin (EASTAR PETG Copolyester 6763, manufactured by Eastman Chemical Co., Ltd., Tg: 79.0 ° C, acid monomer units: terephthalic acid 100 mol ^_0/0, glycol monomer unit: ethylene glycol 68 mol ^_0/0, 1, 4 Cyclohexanedicarboxylic methanol 32 moles to Shikuro ^_0/0, the average refractive index: 1.5667 ) (Hereinafter simply referred to as "PET-2") 0.2 parts by mass of silica (average particle size: 3 ^) is added to 100 parts by mass to form a resin composition. Next, polycarbonate-based As the fat (b-l), a dried aromatic polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., Nonolex 7025A, Tg: 149.5 ° C, average refractive index: 1.5858) (hereinafter simply referred to as “ PC ") and 50% by mass, and as a polyester resin (b-2), a dried transparent soft polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianite DN-124, Tg: 19.1 °) C, a carboxylic acid monomer unit: terephthalic acid 100 mol ^_0/0, glycol monomer unit: ethylene glycol 66 mol ^_0/0, diethylene glycol 2 mol ^_0/0, 1, 4 Kisanjimetano to Shikuro Le 26 mole ^_0/0 , number average molecular weight 1000 polytetramethylene glycol 6 mole ^_0/0, the average refractive index: 1.5461, intrinsic viscosity: 0. 94dl / g) (hereinafter, abbreviated as "PET-1") and 50 wt% Was formed. (A) A resin composition is used as a raw material for a layer, and (B) A mixed resin composition is used as a raw material for a layer. These resin composition and the mixed resin composition are separately separated in the same direction by φ40 mm. After charging into a twin-screw extruder (LZD = 36) and melting and mixing at a set temperature of 270 ° C, the thickness ratio of each layer is (A) layer Z (B) layer Z (A) layer = 1Z4Z1 3 It was co-extruded from a layer die, taken up with a cast roll at 50 ° C, and cooled and solidified to obtain an unstretched laminated sheet having a width of 500 mm and a thickness of 150 m. Next, in the tenter stretching equipment, the sheet is stretched 3.0 times in the transverse uniaxial direction at a preheating temperature of 110 ° C and a stretching temperature of 95 ° C, and then rapidly cooled with cold air to obtain a heat-shrinkable laminated sheet having a thickness of 50 m. Got. The obtained heat-shrinkable laminated sheet was evaluated for glass transition temperature, mechanical properties, and the like. Table 6 shows the results.

Comprehensive evaluation was also performed on the obtained results. Sheets that did not have any problem with all of the evaluation items were indicated by a symbol (〇), and sheets that had at least one problem were indicated by a symbol (X).

(Example IV-2)

As shown in Table 6, as a thermoplastic polyester resin (a-1), 85 parts by mass of PET-2 used in Example IV-1 and polybutylene terephthalate resin [Mitsubishi Engineering Plastics Co., Ltd.] Ltd., NOVADUR5008, carboxylic acid monomer units: terephthalic acid 100 mol ^_0/0, glycol monomer units: 1, 4-butanediol 100 mol ^_0/0, mp: 225 ° C, unique viscosity: 0. 84Dl / g] (hereinafter simply referred to as “PET-4”) 0.2 parts by mass of silica (average particle size: 3) was added to 15 parts by mass to form a resin composition. This resin composition is a raw material for the (A) layer. Next, as the polycarbonate resin (b-1), a mixed resin composition comprising 60% by mass of the PC used in Example IV-1 and 40% by mass of PET-1 was formed. This mixed resin composition is a raw material for the layer (B). These raw materials were put into separate φ40mm co-rotating twin-screw extruders (LZD = 36), melt-mixed at a set temperature of 270 ° C, and the thickness ratio of each layer was changed to (A) layer Z (B) layer The Z (A) layer was co-extruded from a three-layer die so as to be 1Z4Z1, taken with a cast roll at 50 ° C, and cooled and solidified to obtain an unstretched laminated sheet having a width of 500 mm and a thickness of 150 μm. Next, in the tenter stretching equipment, after stretching 3.0 times in the transverse uniaxial direction at a preheating temperature of 110 ° C and a stretching temperature of 95 ° C, it is quenched with cold air to produce a heat-shrinkable laminated sheet having a thickness of 50 m. Obtained. The same evaluation as in Example 1 was performed on the obtained heat-shrinkable laminated sheet. Table 6 shows the results.

[0181] (Comparative Example IV-1)

As shown in Table 6, the same procedure as in Example IV-1 was carried out except that the intermediate layer (B) was not provided in Example IV-1. The resin composition is placed in a φ40mm co-rotating twin screw extruder (LZD = 36), melt-mixed at a set temperature of 270 ° C, extruded from a single-layer die, taken up with a 50 ° C cast roll, and cooled. It was solidified to obtain an unstretched sheet having a width of 500 mm and a thickness of 150 m. Next, the film is stretched 3.0 times in the transverse uniaxial direction at a preheating temperature of 110 ° C and a stretching temperature of 95 ° C in a tenter stretching facility, and then rapidly cooled with cold air to obtain a heat-shrinkable sheet having a thickness of 50 m. Was. The same evaluation as in Example IV-1 was performed on the obtained heat-shrinkable sheet. Table 6 shows the results.

[0182] [Table 6]

Implementation 1 row IV ratio ^ Example IV

1 2 1

PET-2 (% by mass) 100 85 100

P ET- 4 (mass ^_0/0) 15

PC (% by mass) 50 60 ―

PET-1 (mass%) 50 40 ―

Stretching temperature c) 95 95 95

S elongation 3.0 3.0 3.0

(B) Tg C ° c of layer 64.2 76.5 Mixed resin composition 裀

(Single) (single)

Haze (%) 2.8 2.9 2.2 Heat shrinkage [%] 48.8 42.3 54.6

0.6 0.5 0,5 Storage modulus (Ε ') (MP a) 2118 2253 1831

O 仕 X

Sewing machine

Total evaluation 〇〇 X

[0183] As is clear from Table 6, the heat-shrinkable laminated sheet of the present invention having a predetermined (A) layer constituting both outer layers and a predetermined (B) layer located between both outer layers ( Examples IV-1 and IV-2) were found to have a small natural shrinkage, excellent shrinkage finish, transparency, sheet waist (rigidity at room temperature), and excellent perforation cutability ( Example IV-1, Example IV-2). On the other hand, as in Comparative Example IV-1, a single-layer heat-shrinkable sheet composed of only the layer (A) is excellent in the evaluation of the transparency and the natural shrinkage, but the shrinkage is small. It was a component that was inferior in finish and perforation cutability.

Further, the heat-shrinkable laminated sheet of the present invention (the sheet of Example IV-1 and Example IV-2) can be obtained by adding recycled resin to the raw materials of the (A) layer and the Z or (B) layer. A sheet having good compatibility and excellent transparency was obtained. That is, it was a component that the heat-shrinkable laminated sheet of the present invention was also excellent in the recyclability.

Industrial applicability

[0184] The resin composition of the present invention has excellent mechanical properties such as transparency, impact resistance, fluidity, and elongation at break, and has secondary workability and the like in the same temperature range as PVC resin. Because of this, it can be applied to a wide range of applications, and is suitably used for applications where PVC resin has been used conventionally. For example, it is applied to building materials, interior parts, transparent sheets, resin-coated metal plates, molding sheets, colored plates, transparent plates, heat-shrinkable sheets, molded products, and the like. The heat-shrinkable sheet and the heat-shrinkable laminated sheet of the present invention are used for applications such as shrink wrapping, shrink wrapping, and shrink labels.

Brief Description of Drawings

FIG. 1 is a DSC thermogram showing a glass transition temperature (Tg) of a sheet obtained in Example I4.

FIG. 2 is a DSC thermogram showing a glass transition temperature (Tg) of the sheet obtained in Comparative Example I2.

FIG. 3 is a diagram showing loss tangent (tan δ) curves of Examples II I and II 2 and Comparative Examples II 1 and II 3

Claims

The scope of the claims

[1] Polycarbonate resin (b-1) 1% to 99% by mass and polyester resin

(b-2) In the mixed resin composition comprising not less than 1% by mass and not more than 99% by mass, the polyester resin (b-2) force The monomer unit (a) contains an aromatic dicarboxylic acid unit in an amount of 80 mol% or more and 100 mol% or less, and has a glycol monomer unit (mouth) of 1, 4 in all glycol monomer units (mouth). and 40 mol% or less Cyclohexanedicarboxylic methanol units 0.1 mol% or more to Shikuro, contains a number average molecular weight of 500 or more 3,000 or less polyalkylene glycol unit 0.5 mole ^_0/0 to 15 mole ^_0/0 or less A mixed resin composition characterized in that it is a polyester resin.

[2] The mixed resin composition according to claim 1, wherein the polycarbonate resin (b-1) is an aromatic polycarbonate resin.

[3] The polyester resin (b-2) has a glass transition temperature of 0 ° C or more and 50 ° C or less measured at a heating rate of 10 ° CZ by differential scanning calorimetry. Item 3. The mixed resin composition according to Item 1 or 2.

[4] The mixed resin composition has a single glass transition temperature measured at a heating rate of 10 ° CZ by differential scanning calorimetry, and has a glass transition temperature of the polycarbonate resin (b-1). The mixed resin according to any one of claims 1 to 3, wherein the temperature is located between the glass transition temperature of the polyester resin and the glass transition temperature of the polyester resin (b-2). Composition.

[5] The mixed resin composition according to any one of claims 1 to 4, wherein the glass transition temperature measured at a heating rate of 10 ° CZ by differential scanning calorimetry is 50 ° C to 100 ° C. 3. The mixed resin composition according to item 1.

[6] The mixed resin composition according to any one of claims 1 to 4, wherein a glass transition temperature measured at a heating rate of 10 ° CZ by differential scanning calorimetry is 100 ° C to 150 ° C. 2. The mixed resin composition according to item 1, V.

[7] The mixed resin composition comprises 75% by mass or more and 95% by mass or less of the polycarbonate resin (b-l) and 5% by mass or more and 25% by mass or less of the polyester resin (b-2). The mixed resin composition according to any one of claims 1 to 6, comprising:

[8] The mixed resin composition comprises the polycarbonate resin (bl) in an amount of from 60% by mass to 95% by mass, and the polyester resin (b-2) in an amount of from 5% by mass to 40% by mass. The mixed resin composition according to any one of claims 1 to 6, comprising:

[9] The mixed resin composition comprises 30% by mass or more and 75% by mass or less of the polycarbonate resin (b-l) and 25% by mass or more and 75% by mass or less of the polyester resin (b-2). The mixed resin composition according to any one of claims 1 to 6, comprising:

[10] The mixed resin composition comprises 30% by mass or more and 70% by mass or less of the polycarbonate resin (bl) and 30% by mass or less and 70% by mass or less of the polyester resin (b-2). The mixed resin composition according to any one of claims 1 to 6, comprising:

[11] A sheet comprising the mixed resin composition according to any one of claims 1 to 10.

[12] A sheet formed using the mixed resin composition according to claim 10 is stretched in at least one direction and immersed in hot water at 80 ° C for 10 seconds for at least one direction. A heat-shrinkable sheet characterized by at least 20%.

[13] A loss tangent (tan δ) curve obtained by performing dynamic viscoelasticity measurement at a vibration frequency of 10 Hz has a single peak within a range of 70 ° C to 130 ° C, and the loss tangent curve 13. The heat-shrinkable sheet according to claim 12, wherein a half width of the heat-shrinkable sheet is 15 ° C. or more.

[14] It has a layer (A) constituting both outer layers and a layer (B) located between both outer layers, is stretched in at least one axial direction, and is immersed in warm water of 80 ° C for 10 seconds. A heat-shrinkable laminated sheet having a heat shrinkage ratio of 20% or more in the main shrinkage direction at the time, wherein the (A) layer strength is a resin composition mainly composed of _a thermoplastic polyester resin ( _a -1). 11. A heat-shrinkable laminated sheet, characterized in that the layer (B) is made of the mixed resin composition according to claim 10.

[15] The thermoplastic polyester榭脂(a- 1) 1S thermoplastic polyester榭脂(a- 1) 1 in the whole glycol monomer unit in the 4 Cyclohexanedicarboxylic methanol unit 15 mol ⁰ to Shikuro / ₀ or more heat-shrinkable laminated sheet according to請Motomeko 14 is an amorphous polyethylene terephthalate榭脂containing 50 mol% or less.

[16] A sheet for a resin-coated metal sheet, comprising the mixed resin composition according to claim 8.

[17] The method for producing a resin-coated metal sheet according to claim 16, wherein the temperature of the mixed resin composition is higher by 10 ° C than the flow starting temperature (T1) by a calendering method. A method for producing a sheet for a resin-coated metal sheet, comprising forming the sheet at a temperature from (T1 + 10 ° C) to 200 ° C.

[18] A resin-coated metal plate coated with the resin-coated metal sheet sheet according to claim 16.

[19] A shrinkable label using the heat-shrinkable sheet according to claim 12 or 13 or the heat-shrinkable laminated sheet according to claim 14 or 15.

[20] A package equipped with the shrink label according to claim 19.

[21] A molded article using the mixed resin composition according to any one of claims 1 to 10.